Curable fluorine-containing polymer, curable resin composition prepared from same and antireflection film

ABSTRACT

A curable fluorine-containing polymer having a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (1): -(A)-(M)- in which the structural unit M is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (M): [—(CX 1 X 2 —CX 3 )—]—(CX 4 CX 5 ) a —(C═O) b (O) c —Rf, wherein X 1  and X 2  are the same or different and each is H or F; X 3  is H, F, CH 3  or CF 3 ; X 4  and X 5  are the same or different and each is H, F or CF 3 ; Rf is an organic group as defined herein; a is 0 or an integer of from 1 to 3; b and c are the same or different and each is 0 or 1, and the structural unit A is derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer from which M is derived.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No. 11/226,355filed Sep. 15, 2005, which is a Continuation of U.S. application Ser.No. 10/362,719 filed Feb. 26, 2003, which is a 371 of PCT ApplicationNo. PCT/JP01/07344 filed Aug. 28, 2001; the above-noted applicationsincorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a novel curable fluorine-containingpolymer, a curable resin composition prepared from same and a curedarticle and cured film obtained by curing the curablefluorine-containing polymer and also relates to an antireflection filmobtained from the cured film and an antireflection-treated articleprovided with the antireflection film.

BACKGROUND ART

As a result of development of multi-media, it has become more importantto secure an increased visible area (a property of decreasingsurface-reflected area when viewing at an angle, which is also called“visibility”) of a display of various displaying devices. A large sizedisplaying device is also required to have well visible display, whichis a problem to be solved from technical point of view.

In order to enhance visibility of the displaying device, anantireflection film made of a material having a low refractive index hasbeen formed on a substrate of the displaying device. For forming anantireflection film, there is known, for example, a method of forming athin film of a fluorine-containing compound by a deposition method.However in the deposition method, it is difficult to form a coating filmon a substrate for a large display and yet a cost is high since a vacuumequipment is required.

Such being the case, there have been studied methods of forming anantireflection film by preparing a liquid composition by dissolving afluorine-containing polymer having a low refractive index in an organicsolvent and then coating the obtained composition on a surface of asubstrate (for example, JP6-115023A, etc.).

However in the method of coating the fluorine-containing polymersolution, hardness of a coating film is insufficient and therefore thecoating film is damaged and peeled off due to abrasion, thereby loweringappearance of a display.

Therefore there have been studied methods of preparing a composition bymixing a photo-curable acrylic monomer, for example, afluorine-containing acrylic monomer or a fluorine-containingpolyfunctional acrylic compound to a fluorine-containing polymer havinga low refractive index and after coating the composition, photo-curingthe acrylic monomer (JP7-126552A, JP7-188588A, JP8-48935A, etc.).

However in those methods, hardness of the coating film is stillinsufficient because the fluorine-containing polymer itself which is themain component is not crosslinked. In order to increase the hardness, anamount of the acrylic monomer or the polyfunctional acrylic compound maybe increased, but in that case, a refractive index of the cured film isincreased and an intended reflection reducing effect is lowered. Also inthose methods, the un-reacted acrylic monomer or polyfunctional acryliccompound is apt to remain in the coating film, which causes lowering ofphysical properties of the cured coating film.

Also methods of mixing a fluorine-containing polymer having aphoto-reactive (photo-polymerizable) functional group introduced in itsside chain with an acrylic monomer or polyfunctional acrylic compoundand photo-curing after coating the mixture have been studied (JP 2527186and JP 2543903). However the fluorine-containing polymers describedtherein are high in a refractive index and therefore are insufficient inperformance for an antireflection film. In addition, as the number ofcure sites of the fluorine-containing polymer is increased to increasehardness, a refractive index becomes high and therefore a reflectionreducing effect is further lowered.

An object of the present invention is to provide a curablefluorine-containing polymer which can make its hardness high byphoto-curing while maintaining a low refractive index.

Another object of the present invention is to provide an antireflectionfilm possessing improved scratch resistance and abrasion resistancewhile maintaining a reflection reducing effect and also to provide anantireflection-treated article having such an antireflection filmthereon.

DISCLOSURE OF INVENTION

The present inventors have made intensive studies to achieve thoseobjects and have found novel curable fluorine-containing polymers havingan ethylenic carbon-carbon double bond in its side chain and have foundthat when those polymers are used, a cured article having a highhardness can be obtained while maintaining a low refractive index.

Further the present inventors have found that a cured film of a specificfluorine-containing polymer having a carbon-carbon unsaturated bond atan end of its side chain is useful as an antireflection film having bothof low reflection and high hardness.

The present inventors have completed the present invention mentionedbelow based on the above-mentioned findings.

The first of the present invention relates to a curablefluorine-containing polymer having an ethylenic carbon-carbon doublebond in its side chain.

The curable fluorine-containing polymer of the present invention has anumber average molecular weight of from 500 to 1,000,000 and isrepresented by the formula (1):

MA  (1)

in which the structural unit M is a structural unit derived fromfluorine-containing ethylenic monomer and represented by the formula(M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1,the structural unit A is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomerrepresented by the formula (M),and the structural unit M and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.

The second of the present invention relates to a process for preparing acurable fluorine-containing polymer having a number average molecularweight of from 500 to 1,000,000 which is characterized by esterifying:

fluorine-containing polymer having hydroxyl and represented by theformula (2)

NB  (2)

in which the structural unit N is a structural unit having hydroxyl andderived from fluorine-containing ethylenic monomer and is represented bythe formula (N):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf¹ is an organic group in which 1 to 3 of Y⁵ (Y⁵ is hydroxyl or amonovalent organic group having 1 to 10 carbon atoms and hydroxyl) arebonded to a fluorine-containing alkyl group having 1 to 40 carbon atomsor a fluorine-containing alkyl group having 2 to 100 carbon atoms andether bond; a is 0 or an integer of from 1 to 3; b and c are the same ordifferent and each is 0 or 1,the structural unit (B) is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomer havinghydroxyl which is represented by the above-mentioned formula (N), andthe structural unit N and the structural unit B are contained in amountsof from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively,with an unsaturated carboxylic acid or its derivative having 3 to 10carbon atoms (a total number of carbon atoms including carbon atoms ofY³ is from 3 to 10) and represented by the formula:

HOOCR¹_(f)CX⁶═CX⁷X⁸

wherein R¹ is a divalent organic group which has 1 to 7 carbon atoms andmay be substituted with fluorine atom; X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸are the same or different and each is H or F; f is 0 or 1. The obtainedcurable fluorine-containing polymer is represented by the formula (1a):

M4A  (1a)

in which the structural unit M4 is a structural unit derived from afluorine-containing ethylenic monomer and represented by the formula(M4):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf² is an organic group in which 1 to 3 of Y⁶ having 3 to 10 carbonatoms and represented by the formula:

R²_(g)O(C═O)—(R¹_(f)—CX⁶═CX⁷X⁸

wherein R¹, X⁶, X⁷, X⁸ and f are as defined above; R² is a divalentorganic group which has 1 to 7 carbon atoms and may be substituted withfluorine atom; g is 0 or 1, are bonded to a fluorine-containing alkylgroup having 1 to 40 carbon atoms or a fluorine-containing alkyl grouphaving 2 to 100 carbon atoms and ether bond; a is 0 or an integer offrom 1 to 3; b and c are the same or different and each is 0 or 1,the structural unit A is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomerrepresented by the formula (M4), andthe structural unit M4 and the structural unit A are contained inamounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole,respectively.

The third of the present invention relates to a fluorine-containingresin composition for coating which comprises:

(a) the above-mentioned curable fluorine-containing polymer or any ofthe curable fluorine-containing polymers of claims 2 to 14,(b) an active energy curing initiator which initiates curing with activeenergy, and(c) a solvent, if necessary,and relates to a cured article obtained therefrom, particularly aphoto-cured article and a cured film.

The fourth of the present invention relates to an antireflection film.

The antireflection film is

an antireflection film which is a cured film of a fluorine-containingprepolymer, in which the fluorine-containing prepolymer has:(i) a carbon-carbon unsaturated bond at an end of its side chain, and(ii) a refractive index of not more than 1.40,and a thickness of the cured film is from 0.03 to 0.5 μm;an antireflection film which is a cured film obtained by photo-curing acoating film formed by coating a composition for coating whichcomprises:(d) the above-mentioned fluorine-containing prepolymer,(e) an active energy curing initiator which initiates curing with activeenergy, and(f) a solvent,in which a thickness of the cured film is from 0.03 to 0.5 μm; oran antireflection film which is a cured film obtained by photo-curing acoating film formed by coating a composition for coating whichcomprises:(d) the above-mentioned fluorine-containing prepolymer,(e) an active energy curing initiator which initiates curing with activeenergy,(f) a solvent, and(g) a curing agent,in which a thickness of the cured film is from 0.03 to 0.5 μm.

The fifth of the present invention relates to an antireflection-treatedarticle obtained by applying the above-mentioned antireflection film ona substrate.

The sixth of the present invention relates to a novelfluorine-containing unsaturated compound. The novel compound is afluorine-containing unsaturated compound represented by the formula(4-1):

CX¹X²═CX³—(CX⁴X⁵)_(a)—(O)_(c)—Rf′  (4-1)

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf′ is an organic group in which 1 to of 3 Y³ (Y³ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or 1,in which Y³ is an organic group represented by the formula:

—(O)_(d)—(C═O)—Y⁴

wherein Y⁴ is an alkenyl group or fluorine-containing alkenyl grouphaving 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond atits end and d is 0 or 1.

BEST MODE FOR CARRYING OUT THE INVENTION

The curable fluorine-containing polymer of the first invention is, asmentioned above, the curable fluorine-containing polymer which has anumber average molecular weight of from 500 to 1,000,000 and isrepresented by the formula (1):

MA  (1)

in which the structural unit M is a structural unit represented by theformula (M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1,the structural unit A is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomerrepresented by the formula (M), andthe structural unit M and the structural unit A are contained in amountsof from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.

The structural unit M is a structural unit derived from afluorine-containing ethylenic monomer represented by the formula (3):

CX¹X²═CX³—(CX⁴X⁵)_(a)—(C═O)_(b)—(O)_(c)—Rf  (3)

wherein X¹, X², X³, X⁴, X⁵, Rf, a, b and c are as defined in the formula(M).

Namely, the curable fluorine-containing polymer is a homopolymer of theabove-mentioned fluorine-containing ethylenic monomer having, in itsside chain, an ethylenic carbon-carbon double bond curable by a reactionor a copolymer having the fluorine-containing ethylenic monomer as anessential component.

It is preferable that at least one of Y¹ is bonded to an end of Rf.

In the curable fluorine-containing polymer of the formula (1) of thepresent invention, the structural unit M is preferably a structural unitM1 represented by:

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or 1.

The structural unit M1 is a structural unit derived from afluorine-containing ethylenic monomer represented by:

CX¹X²═CX³—(CX⁴X⁵)_(a)—(O)_(c)—Rf  (4)

wherein X¹, X², X³, X⁴, X⁵, Rf, a and c are as defined in the formula(3). Among the fluorine-containing unsaturated compounds represented bythe formula (4), the fluorine-containing unsaturated compoundrepresented by the formula (4-1):

CX¹X²═CX³—(CX⁴X⁵)_(a)—(O)_(c)—Rf′  (4-1)

wherein X¹, X², X³, X⁴, X⁵, a and c are as defined in the formula (4);Rf′ is an organic group in which 1 to 3 of Y³ (Y³ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond,in which Y³ is an organic group represented by the formula:

—(O)_(d)—(C═O)—Y⁴

wherein Y⁴ is an alkenyl group or fluorine-containing alkenyl grouphaving 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond atits end, d is 0 or 1,is a novel compound which has not been disclosed in any publications.

The polymer containing the above-mentioned structural unit M1 isparticularly low in refractive index, and is preferred particularlysince a refractive index can be decreased even in the cases of a M1homopolymer and a polymer containing the M1 in an increased amount.

More preferable example of M1 is a structural unit M2 represented by:

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.

The structural unit M2 is a structural unit derived from afluorine-containing ethylenic monomer represented by the formula (4-2):

CH₂═CF—CF₂—O—Rf  (4-2)

wherein Rf is as defined in the formula (3). Among thefluorine-containing unsaturated compounds represented by the formula(4-2), a fluorine-containing unsaturated compound represented by theformula (4-3):

CH₂═CFCF₂ORf′  (4-3)

wherein Rf′ is as defined in the formula (4-1), is a novel compoundwhich has not been disclosed in any publications.

Namely, the above-mentioned M2 is a structural unit of afluorine-containing allyl ether having an ethylenic carbon-carbon doublebond at its end and is preferred since not only a refractive index canbe decreased but also polymerizability thereof, particularlyhomo-polymerizability and copolymerizability with thefluorine-containing ethylenic monomer are good.

Another example of preferable M1 is a structural unit M3 represented by:

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.

The structural unit M3 is a structural unit derived from afluorine-containing ethylenic monomer represented by the formula (4-4):

CF₂═CF—O—Rf  (4-4)

wherein Rf is as defined in the formula (3). Among thefluorine-containing unsaturated compounds represented by the formula(4-4), the fluorine-containing unsaturated compound represented by theformula (4-5):

CF₂═CFORf′  (4-5)

wherein Rf′ is as defined in the formula (4-1) is a novel compound whichhas not been disclosed in any publications.

The above-mentioned M3 is a structural unit of a fluorine-containingvinyl ether having an ethylenic carbon-carbon double bond at its end andis preferred since a refractive index can be decreased andcopolymerizability with the fluorine-containing ethylenic monomer isgood.

In the curable fluorine-containing polymer of the formula (1) of thepresent invention, Y¹ contained in the structural units M, M1, M2 and M3is an organic group having 2 to 10 carbon atoms and an ethyleniccarbon-carbon double bond at its end.

Namely, the carbon-carbon double bond in Y¹ has an ability of causingpolycondensation reaction, ring formation reaction and additionreaction, and thereby a cured (crosslinked) article can be obtained.Concretely, for example, by contact of the carbon-carbon double bondwith radical or cation, there arise a polymerization reaction andcondensation reaction between molecules of the curablefluorine-containing polymer of the present invention or between thecurable fluorine-containing polymer and the curing (crosslinking) agentadded as case demands, and thus a cured (crosslinked) article can beobtained.

In the curable fluorine-containing polymers of the formulae (1) and (2)of the present invention, preferable Y¹ is:

O_(d)C═O_(e)Y²

wherein Y² is an alkenyl group or fluorine-containing alkenyl grouphaving 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond atits end, d and e are the same or different and each is 0 or 1, andpreferable Y² is:

—CX⁶═CX⁷X⁸

wherein X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸ are H or F since curingreactivity thereof by contact with radical or cation is high.

Examples of the preferable Y⁴ in the novel fluorine-containingunsaturated compounds of the present invention represented by (4-1),(4-3) and (4-5) are the same as the above-mentioned Y².

Examples of the preferable Y² and Y⁴ are:

Examples of more preferable Y¹ and Y³ are:

—O(C═O)CX⁶═CX⁷X⁸

wherein X⁶ is H, F, CH₃ or CF₃, X⁷ and X⁸ are H or F, which arepreferred since a curing reactivity by contact with radical isparticularly higher and a cured article can be obtained easily byphoto-curing, etc.

Examples of the above-mentioned Y¹ and Y³ are:

and the like.

Other examples of Y¹ are:

and the like.

Other examples of Y³ are:

and the like.

Particularly those which have a structure of —O(C═O)CF═CH₂ are preferredsince a refractive index can be reduced and a curing (crosslinking)reactivity is particularly high, which enables a cured article to beobtained effectively.

In Rf contained in the structural units M, M1, M2 and M3 of the curablefluorine-containing polymer of the formula (1) of the present invention,Rf′ contained in the novel fluorine-containing unsaturated compoundsrepresented by the formulae (4-1), (4-3) and (4-5), Rf¹ contained in thestructural unit N of the fluorine-containing polymer of the formula (2)having hydroxyl and further Rf⁴ and Rf⁵ contained in the structuralunits (A1) and (A2) of the curable fluorine-containing polymer of theformula (1-1), examples of preferable organic groups excluding thefunctional groups Y¹, Y³, Y⁵, Z¹ and Z² are fluorine-containing alkylenegroups having 1 to 40 carbon atoms and fluorine-containing alkylenegroups having 2 to 100 carbon atoms and ether bond particularly in casewhere the number of functional groups Y¹, Y³ or Y⁵ is one. In thoseorganic groups, fluorine atom is bonded to carbon atom containedtherein. Generally those organic groups are fluorine-containing alkylenegroups or fluorine-containing alkylene groups having ether bond, inwhich fluorine atom and hydrogen atom or chlorine atom are bonded tocarbon atom. Preferred are those having more fluorine atoms (a higherfluorine content). The fluorine content is not less than 50%, preferablynot less than 70% on the basis of a molecular weight of the organicgroups provided that oxygen atoms in the organic groups and thefunctional groups are eliminated from calculation. More preferred areperfluoro alkylene groups or perfluoro alkylene groups having etherbond. Those organic groups are preferred since a refractive index of thecurable fluorine-containing polymer can be reduced, particularly since alow refractive index can be maintained even when a curing degree(density of crosslinking) is made high to increase hardness of the curedarticle.

Too large number of carbon atoms is not preferable because in case ofthe fluorine-containing alkylene groups, there is a case wheresolubility in a solvent is lowered and transparency is lowered and incase of the fluorine-containing alkylene groups having ether bond, thereis a case where hardness and mechanical properties of the polymer itselfand the cured article obtained therefrom are lowered. The number ofcarbon atoms of the fluorine-containing alkylene groups is preferablyfrom 1 to 20, more preferably from 1 to 10, and the number of carbonatoms of the fluorine-containing alkylene groups having ether bond ispreferably from 2 to 30, more preferably from 2 to 20

Preferable example thereof is:

(m: from 1 to 10, n: from 0 to 5)

(l: from 1 to 10, m: from 1 to 10, n: from 0 to 5)

(X⁹ and X^(9′) are F or CF₃; X¹⁰ and X^(10′) are H or F; o+p+q is from 1to 30; r is 0 or 1; s and t are 0 or 1).

Mentioned below are structures of the structural unit M constituting thecurable fluorine-containing polymer of the present invention andexamples of the novel fluorine-containing unsaturated compound.

Examples of the preferable monomer giving the structural unit M2 are:

(n: an integer of from 1 to 30)

(n: an integer of from 1 to 30)

and the like. More concretely there are:

(X is H, CH₃, F or CF₃; n is 0 or an integer of from 1 to 30)

(n is 0 or an integer of from 1 to 30)

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms; n is0 or an integer of from 1 to 30)

(X is H, CH₃, F or CF₃; n is 0 or an integer of from 1 to 30)and the like.

Preferable examples of the novel fluorine-containing unsaturatedcompound of the formula (4-3) are those exemplified above as the monomergiving the structural unit M2, in which Y¹ is replaced with Y³.

More concretely there are:

(X is H, CH₃, F or CF₃; n is 0 or an integer of from 1 to 30)

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms; n is0 or an integer of from 1 to 30)

(X is H, CH₃, F or CF₃; n is 0 or an integer of from 1 to 30)and the like.

Examples of the preferable monomer giving the structural unit M3 are:

(n is from 1 to 30)

and the like.

More concretely there are:

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms)

(m is from 0 to 30, n is from 1 to 3, X is H, CH₃, F or CF₃)and the like.

Preferable examples of the novel fluorine-containing unsaturatedcompound of the formula (4-5) are those exemplified above as the monomergiving the structural unit M3, in which Y¹ is replaced with Y³.

More concretely there are:

(Rf¹ and Rf² are perfluoroalkyl groups having 1 to 5 carbon atoms)

(m is from 0 to 30, n is from 1 to 3, X is H, CH₃, F or CF₃)and the like.

Examples of a preferable monomer constituting the structural unit M ofthe curable fluorine-containing polymer of the present invention otherthan M2 and M3 are, for instance,

and the like, wherein Rf is as defined above.

More concretely there are:

and the like.

In the novel fluorine-containing unsaturated compounds of the formula(4-1) of the present invention, preferred examples of thefluorine-containing unsaturated compounds other than those of theabove-mentioned formulae (4-3) and (4-5) are the monomers exemplifiedabove as the monomers giving the structural unit M other than thestructural units M2 and M3, in which Y¹ is replaced by Y³.

In the curable fluorine-containing polymer of the present invention, thestructural unit A is an optional component and is not limitedparticularly as far as it is a monomer copolymerizable with thestructural unit M, M1, M2 or M3. The structural unit A may be selectedoptionally depending on intended applications and requiredcharacteristics of the curable fluorine-containing polymer and the curedarticle obtained therefrom.

Examples of the structural unit A are, for instance,

{circle around (1)} Structural Units (A1) Derived fromFluorine-Containing Ethylenic Monomers Having Functional Group

These structural units are preferred from the point that adhesion to asubstrate and solubility in a solvent, particularly a general-purposesolvent are imparted to the curable fluorine-containing polymer whilemaintaining a low refractive index of the polymer and the cured articleobtained therefrom and in addition, characteristics such ascrosslinkability other than those influenced by Y are imparted to thepolymer. The structural unit of the fluorine-containing ethylenicmonomers having functional group is represented by the formula (A1):

wherein X¹¹, X¹² and X¹³ are H or F; X¹⁴ is H, F or CF₃, h is 0, 1 or 2;i is 0 or 1; Rf⁴ is a fluorine-containing alkylene group having 1 to 40carbon atoms or a fluorine-containing alkylene group having 2 to 100carbon atoms and ether bond; Z¹ is selected from —OH, —CH₂OH, —COOH,carboxylic acid derivative, —SO₃H, sulfonic acid derivative, epoxy groupand cyano group. Particularly preferred is the structural unitrepresented by the formula (A1-1):

wherein Rf⁴ and Z¹ are as defined in the formula (A1).

Concretely preferred are structural units derived fromfluorine-containing ethylenic monomers such as:

Also there are preferable structural units represented by the formula(A1-2):

wherein Rf⁴ and Z¹ are as defined in the formula (A1).

Concretely preferred are structural units derived from monomers such as:

Examples of other fluorine-containing ethylenic monomers havingfunctional group are:

CF₂═CFCF₂—O—Rf—Z¹, CF₂═CF—Rf—Z¹,

CH₂═CH—Rf—Z¹, CH₂═CHO—Rf—Z¹ and the like,

wherein Rf is the same as Rf of the formula (M).

Concretely there are:

and the like.{circle around (2)} Structural Units (A2) Derived fromFluorine-Containing Ethylenic Monomers not Having Functional Group

These structural units are preferred from the point that a refractiveindex of the curable fluorine-containing polymer or the cured articleobtained therefrom can be kept low and the refractive index can befurther reduced. Also those structural units are preferred sincemechanical properties, glass transition temperature, etc. of the polymercan be adjusted by selecting monomers, particularly since the glasstransition temperature can be increased by copolymerizing with thestructural unit M.

Preferred structural units of the fluorine-containing ethylenic monomersare those represented by the formula (A2):

wherein X¹⁵, X¹⁶ and X¹⁸ are H or F; X¹⁷ is H, F or CF₃; h1 and i1 and jare 0 or 1; Z² is H, F or Cl; Rf⁵ is a fluorine-containing alkylenegroup having 1 to 20 carbon atoms or a fluorine-containing alkylenegroup having 2 to 100 carbon atoms and ether bond.

Preferred examples thereof are structural units derived from monomerssuch as:

(n: from 1 to 5), CH₂═C(CF₃)₂,

(n: from 0 to 10),CH₂═CFCF₂_(n)Z² (Z² is as defined in the formula (A2), n: from 1 to10), CH₂═CHOCH₂CF₂_(n)Z² (Z² is as defined in the formula (A2), n:from 1 to 10) .{circle around (3)} Fluorine-Containing Aliphatic Ring Structural Units(A3)

The introduction of these structural units is preferred sincetransparency can be increased, a refractive index can be made lower andfurther the curable fluorine-containing polymer having a high glasstransition temperature can be obtained and a higher hardness of thecured article can be expected.

Preferred fluorine-containing aliphatic ring structural units are thoserepresented by the formula (A3):

wherein X¹⁹, X²⁰, X²³, X²⁴, X²⁵ and X²⁶ are the same or different andeach is H or F; X²¹ and X²² are the same or different and each is H, F,Cl or CF₃; Rf⁶ is a fluorine-containing alkylene group having 1 to 10carbon atoms or a fluorine-containing alkylene group having 2 to 10carbon atoms and ether bond; n2 is 0 or an integer of from 1 to 3; n1,n3, n4 and n5 are the same or different and each is 0 or 1.

For example, there are structural units represented by:

wherein Rf⁶, X²¹ and X²² are as defined above.

Concretely there are:

and the like.{circle around (4)} Structural Units Derived from Ethylenic Monomers notHaving Fluorine

The structural units derived from ethylenic monomers not having fluorinemay be introduced to the polymer in a range where the introduction doesnot have an adverse effect on a refractive index (in a range where therefractive index does not increase).

The introduction of those structural units is preferred since solubilityin a general-purpose solvent is enhanced and compatibility withadditives, for example, a photocatalyst and a curing agent to be addedas case demands can be improved.

Examples of the non-fluorine-containing ethylenic monomer are asfollows.

α-Olefins:

Ethylene, propylene, butene, vinyl chloride, vinylidene chloride and thelike.

Vinyl Ether or Vinyl Ester Monomers:

CH₂═CHOR, CH₂═CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms)and the like.

Allyl Monomers:

CH₂═CHCH₂Cl, CH₂═CHCH₂OH, CH₂═CHCH₂COOH,

CH₂═CHCH₂Br and the like.

Allyl Ether Monomers:

CH₂═CHCH₂OR

(R: hydrocarbon group having 1 to 20 carbon atoms),

and the like.

Acrylic or Methacrylic Monomers:

Acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acidesters, maleic anhydride, maleic acid, maleic acid esters and the like.

{circle around (5)} Structural Units Derived from Alicyclic Monomers

A structural unit of an alicyclic monomer may be introduced as acomponent copolymerizable with the structural unit M, more preferably asthe third component in addition to the structural unit M and thestructural unit of the above-mentioned fluorine-containing ethylenicmonomer or non-fluorine-containing ethylenic monomer (theabove-mentioned {circle around (3)} and {circle around (4)}), which ispreferable since a high glass transition temperature can be obtained andhardness can be increased.

Examples of the alicyclic monomer are norbornene derivatives representedby:

wherein m is from 0 to 3; A, B, C and D are H, F, Cl, COOH, CH₂OH, aperfluoroalkyl having 1 to 5 carbon atoms or the like, alicyclicmonomers such as:

and derivatives thereof in which a substituent is introduced.

In the curable fluorine-containing polymer of the present invention,various combinations and proportions of the structural units M (M1, M2and M3) and A can be selected from the above-mentioned examplesdepending on intended applications, physical properties (particularlyglass transition temperature, hardness, etc.), functions (transparencyand refractive index) and the like.

The curable fluorine-containing polymer of the present inventioncontains the structural unit M (M1, M2 or M3) as an essential componentand is characterized in that the structural unit M itself has functionsof maintaining a low refractive index and imparting transparency to thepolymer and functions of imparting hardness, abrasion resistance,scratch resistance and solvent resistance to the cured article bycuring. Therefore even if the curable fluorine-containing polymer of thepresent invention contains a larger amount of the structural unit M orin the extreme case, even if the polymer consists of the structural unitM (100% by mole), the low refractive index can be maintained. Furtherthe curable fluorine-containing polymer of the present invention ispreferred since the cured article having a high curing (crosslinking)density and the coating film having a high hardness and excellentabrasion resistance and scratch resistance can be obtained.

Also in the case of the copolymer of the present invention comprisingthe structural unit M and the structural unit A of the copolymerizablemonomer, when the structural unit A is selected from the above-mentionedexamples, the polymer which provides the cured article having a higherhardness (high glass transition temperature) and a low refractive indexcan be obtained.

In the copolymer comprising the structural unit M and the structuralunit A, the proportion of the structural unit M may be not less than0.1% by mole based on the whole monomers constituting the curablefluorine-containing polymer. It is preferable that the proportion is notless than 2.0% by mole, more preferably not less than 5% by mole,further preferably not less than 10% by mole in order to obtain thecured article having a high hardness, excellent abrasion resistance andscratch resistance and good chemical resistance and solvent resistanceby curing (crosslinking).

Particularly for the antireflection film application which requiresformation of a cured coating film having excellent scratch and damageresistance, it is preferable that the structural unit M is contained inan amount of not less than 10% by mole, preferably not less than 20% bymole, more preferably not less than 50% by mole.

The curable fluorine-containing polymer of the present invention ispreferable particularly for the antireflection film application since areflection reducing effect is not lowered even if the proportion of thestructural unit M is increased (or even if the number of cure sites isincreased).

Also in case of the antireflection film application, etc. requiringtransparency, preferred combinations and proportions of the structuralunits M and A are those which can make the curable fluorine-containingpolymer non-crystalline.

Preferred fluorine-containing polymers for a coating composition aimingat a low refractive index and a high hardness are curablefluorine-containing polymers represented by the formula (1-1).

-(M)-(A1)-(A2)-  (1-1)

The structural unit M in the formula (1-1) is the above-mentionedstructural unit having an ethylenic carbon-carbon double bond in itsside chain, and the same structural units as the above-mentionedpreferable examples of the formulae (M1), (M2) and (M3) can be used asthe structural unit M.

The structural unit A1 is derived from a fluorine-containing ethylenicmonomer having functional group in its side chain and is represented bythe formula (A1):

wherein X¹¹, X¹² and X¹³ are H or F; X¹⁴ is H, F or CF₃; h is 0, 1 or 2;i is 0 or 1; Rf⁴ is a fluorine-containing alkylene group having 1 to 40carbon atoms or a fluorine-containing alkylene group having 2 to 100carbon atoms and ether bond; Z¹ is selected from —OH, —CH₂OH, —COOH,carboxylic acid derivative, —SO₃H, sulfonic acid derivative, epoxy groupand cyano group. The above-mentioned examples of the structural unit A1derived from the fluorine-containing ethylenic monomer having functionalgroup can be preferably used similarly.

The structural unit A2 is derived from a fluorine-containing ethylenicmonomer not having functional group and is represented by the formula(A2):

wherein X¹⁵, X¹⁶ and X¹⁸ are H or F; X¹⁷ is H, F or CF₃; h1, i1 and jare 0 or 1; Z² is H, F or Cl; Rf⁵ is a fluorine-containing alkylenegroup having 1 to 20 carbon atoms or a fluorine-containing alkylenegroup having 2 to 100 carbon atoms and ether bond. The above-mentionedexamples of the structural unit A2 derived from the fluorine-containingethylenic monomer not having functional group can be preferably usedsimilarly. Among them, preferred is a structural unit derived from atleast one monomer selected from the group consisting oftetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride andhexafluoropropylene.

It is preferable that the proportions of the structural units M, A1 andA2 are from 0 to 90% by mole, from 0 to 99.9% by mole and from 0 to99.9% by mole, respectively and A1+A2 is from 10 to 99.9% by mole. It isparticularly preferable that the proportions of the structural units M,A1 and A2 are from 10 to 80% by mole, from 1 to 60% by mole and from 20to 85% by mole, respectively and A1+A2 is from 20 to 90% by mole. Whenthe proportion of the structural unit M is too low, hardness of thecured coating film tends to be lowered and strength thereof tends tobecome insufficient. When the proportion of the structural unit A1 istoo low, adhesion and coatability to a substrate and solubility in asolvent tend to become insufficient. When the proportion of thestructural unit A2 is too low, there is a tendency that coatability to asubstrate, leveling property and solubility in a solvent becomeinsufficient.

In the fluorine-containing polymer comprising those structural units M,A1 and A2, hardness, mechanical strength and solvent resistance can beimparted to the cured coating film by a cure site of the structural unitM. Also the functional group of the structural unit A1 can impartadhesion to a substrate, solubility in a solvent and good coatability(wettability and leveling property) to the substrate. Further thestructural unit A2 can impart, to the fluorine-containing polymer, amechanical strength, solubility in a solvent and good coatability to asubstrate.

Further since any of the structural units M, A1 and A2 have manyfluorine atoms, the above-mentioned functions can be imparted whilemaintaining a low refractive index, and therefore the curablefluorine-containing polymer is preferred as a coating agent for anantireflection purpose.

The molecular weight of the curable fluorine-containing polymer of thepresent invention can be selected, for example, in a range of from 500to 1,000,000 in number average molecular weight. Preferred molecularweight is from 1,000 to 500,000, particularly from 2,000 to 200,000.

When the molecular weight is to low, even after the curing, mechanicalproperties are apt to be insufficient, and particularly the curedarticle and cured coating film become fragile and are apt to lackstrength. If the molecular weight is too high, solubility in a solventis lowered, film forming property and leveling property tend to belowered particularly at forming a thin coating film and storagestability of the curable fluorine-containing polymer tends to belowered. For coating applications, most preferable number averagemolecular weight is selected in a range of from 5,000 to 100,000.

In the curable fluorine-containing polymer of the present invention,though various refractive indices can be selected depending on kind andcontent of the structural unit M and kind of the structural unit A to beused as case demands, it is preferable that the refractive index of thecurable fluorine-containing Polymer itself (before curing) is not morethan 1.45, more preferably not more than 1.40, particularly preferablynot more than 1.38. The refractive index changes depending on kinds of asubstrate and undercoating, but since the curing (crosslinking) can bedone while maintaining a low refractive index, the polymer can be apreferable base polymer for an antireflection film.

Also it is preferable that the curable fluorine-containing polymer issoluble in general-purpose solvents, for example, in at least one ofketone solvents, acetic acid ester solvents, alcohol solvents andaromatic solvents or in solvent mixtures containing at least one of theabove-mentioned general-purpose solvents.

When the polymer is soluble in general-purpose solvents, it ispreferable because film forming property and homogeneity are excellentin coating application, particularly in case of forming a thinantireflection film of about 0.1 μm thick on various transparent filmsand displaying substrates. The polymer is also advantageous from theviewpoint of productivity in forming an antireflection film.

In order to obtain the curable fluorine-containing polymer of thepresent invention, any of

{circle around (1)} a method of previously synthesizing a monomer havingthe functional group Y¹ and then polymerizing,{circle around (2)} a method of once synthesizing a polymer havinganother functional group and then converting the functional group byhigh molecular reaction, thus introducing the functional group Y¹ intothe polymer, or the like method can be employed.

In the method {circle around (1)}, in order to obtain the curablefluorine-containing polymer of the present invention having acarbon-carbon double bond in its side chain without reacting (curing)the carbon-carbon double bond at an end of its side chain, it isnecessary to change reactivity of two kinds of double bonds (a doublebond becoming a trunk chain and a double bond becoming a side chain) ina (co)polymerizable monomer and thereby make only one of the doublebonds participate in the polymerization. In such a method, it isdifficult to select the polymerization conditions to obtain the curablefluorine-containing polymer of the present invention having a doublebond in its side chain, and also it is difficult to use a monomer whichgives a high curing reactivity of the double bond in the side chain tothe obtained curable polymer.

On the contrary, the method {circle around (2)} is a preferable methodsince it is easy to obtain the curable fluorine-containing polymer ofthe present invention without curing reaction and also from the pointthat a carbon-carbon double bond having a high curing reactivity can beintroduced to its side chain.

Among the methods {circle around (2)}, there is preferably employed, forexample, a method of obtaining the curable fluorine-containing polymerof the present invention by synthesizing the fluorine-containing polymercomprising the structural unit N of fluorine-containing monomer havinghydroxyl or an organic group Y³ having hydroxyl and as case demands, thestructural unit B of monomer copolymerizable with N, and then reactingthe polymer with an unsaturated carboxylic acid or its derivative tointroduce a carbon-carbon double bond to an end of a side chain of thepolymer.

Therefore the second of the present invention relates to the process forpreparing the curable fluorine-containing polymer, which ischaracterized by esterification reaction, with an unsaturated carboxylicacid or its derivative, of the fluorine-containing polymer havinghydroxyl and represented by the formula (2):

NB  (2)

in which the structural unit N is a structural unit having hydroxyl andderived from a fluorine-containing ethylenic monomer and is representedby the formula (N):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf¹ is an organic group in which 1 to 3 of Y⁵ (Y⁵ is hydroxyl or amonovalent organic group having 1 to 10 carbon atoms and hydroxyl) arebonded to a fluorine-containing alkyl group having 1 to 40 carbon atomsor a fluorine-containing alkyl group having 2 to 100 carbon atoms andether bond; a is 0 or an integer of from 1 to 3; b and c are the same ordifferent and each is 0 or 1,the structural unit B is a structural unit derived from monomercopolymerizable with the fluorine-containing ethylenic monomer havinghydroxyl and represented by the above-mentioned formula (N), andthe structural unit N and the structural unit B are contained in amountsof from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.

In the above-mentioned process for preparing the curablefluorine-containing polymer of the present invention, examples of thepreferable structural unit N of the fluorine-containing polymer havinghydroxyl which is a precursor represented by the formula (2) arestructures which correspond to the above-exemplified respectivestructural units M of the curable fluorine-containing polymer and havethe Y⁵ having OH group instead of the Y¹ having a carbon-carbon doublebond. Those structural units can be used preferably. As the structuralunit B, there can be preferably used the same structural units as theabove-mentioned structural unit A.

The unsaturated carboxylic acid or its derivative which is reacted withthe fluorine-containing polymer having hydroxyl may be any of carboxylicacids or derivatives thereof having a carbon-carbon double bond at anend thereof. Particularly preferred are α,β-unsaturated carboxylic acidsor derivatives thereof (f=0).

Examples thereof are, for instance, carboxylic acids represented by:

wherein R is H, CH₃, F, CF₃ or Cl, or anhydrides thereof, acid halidesrepresented by:

wherein R is as defined above, X is Cl or F, maleic acid, maleicanhydride, maleic acid monoalkylester and the like.

Among them, unsaturated carboxylic acid halides are preferred since thereaction can be carried out at room temperature and gelling of aprepared polymer can be prevented.

Particularly preferred are:

The method of reacting the fluorine-containing polymer having hydroxylwith α,β-unsaturated carboxylic acid halide is not limited particularlyand is usually carried out by dissolving the fluorine-containing polymerhaving hydroxyl in a solvent and mixing the α,β-unsaturated carboxylicacid halide thereto at a temperature of from about −20° C. to about 40°C. with stirring.

In the reaction, through the reaction conditions, HCl and HF areproduced and therefore it is desirable to add a proper base forcapturing them. Examples of the base are tertiary amines such aspyridine, N,N-dimethylaniline, tetramethylurea and triethylamine,magnesium metal and the like. Also an inhibitor may be present toprevent a polymerization reaction of the carbon-carbon double bonds inthe starting α,β-unsaturated carboxylic acid and the obtained curablefluorine-containing polymer during the reaction.

Examples of the inhibitor are hydroquinone, t-butyl hydroquinone,hydroquinone monomethylether and the like.

The fluorine-containing polymer having hydroxyl before the reaction withthe unsaturated carboxylic acid or its derivative can be obtained by(co)polymerizing through known method the respective component unitssuch as the ethylenic monomer (N) having hydroxyl and the monomer (B)when used as a copolymerizable component. For the polymerization,radical polymerization method, anion polymerization method, cationpolymerization method and the like can be employed. Among them, theradical polymerization method is preferably used from the viewpoint thateach monomer exemplified to obtain the polymer having hydroxyl of thepresent invention has good radial polymerizability, control ofcomposition and molecular weight is easy and production in an industrialscale is easy.

In order to initiate the radical polymerization, means for initiation isnot limited particularly as far as the polymerization proceedsradically. The polymerization is initiated, for example, with an organicor inorganic radical polymerization initiator, heat, light, ionizingradiation or the like. The polymerization can be carried out by solutionpolymerization, bulk polymerization, suspension polymerization, emulsionpolymerization or the like. The molecular weight is controlled by thecontents of the monomers to be used for the polymerization, the contentof the polymerization initiator, the content of a chain transfer agent,temperature, etc. The components of the copolymer can be controlled bythe starting monomer components.

The third of the present invention relates to the composition comprisinga curable fluorine-containing polymer. One of the compositions of thepresent invention is the curable fluorine-containing resin compositioncomprising:

(a) a curable fluorine-containing polymer and(b) an active energy curing initiator which initiates curing with activeenergy.

The curable fluorine-containing polymer (a) for the composition of thepresent invention is the above-mentioned curable fluorine-containingpolymer having a carbon-carbon double bond in its side chain, andpreferred examples thereof are the same as those exemplified above.

The active energy curing initiator (b) which initiates curing withactive energy functions as a catalyst which generates radical or cationonly by irradiation of, for example, an electromagnetic wave having awavelength of not more than 350 nm, namely ultraviolet light, electronbeam, X-ray, γ-ray and the like and initiates curing (crosslinkingreaction) of the carbon-carbon double bond of the curablefluorine-containing polymer. Usually curing initiators which generateradical or cation by irradiation of ultraviolet light, particularlythose generating radical are used.

This curable fluorine-containing resin composition can initiate a curingreaction easily with the above-mentioned active energy, does not requireheating at high temperatures and can be subjected to the curing reactionat low temperatures. Therefore the composition is preferred from thepoint that it can be used on substrates, for example, transparent resinsubstrates which have low heat resistance and easily undergodeformation, degrading and coloring due to heat.

In the composition of the present invention, the curing initiator (b)which initiates curing with active energy is optionally selecteddepending on kind of the carbon-carbon double bond (radical-reactivityor cation-reactivity) in the side chain of the curablefluorine-containing polymer (a), kind (wavelength range, etc.) of theactive energy, intensity of irradiation, etc. Generally examples of theinitiator which functions to initiate curing of the curablefluorine-containing polymer (a) having a radical-reactive carbon-carbondouble bond with active energy in an ultraviolet region are, forinstance, those mentioned below.

Acetophenone Initiators

Acetophenone, chloroacetophenone, diethoxyacetophenone,hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropane-1-one and thelike.

Benzoin Initiators

Benzoin, benzoinmethylether, benzoinmethylether, benzoinisopropylether,benzoinisobutylether, benzyldimethylketal and the like.

Benzophenone Initiators

Benzophenone, benzoyl benzoate, methyl-o-benzoylbenzoate,4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone,acrylated benzophenone, Michler's ketone and the like.

Thioxanthone Initiators

Thioxanthone, chlorothioxanthone, methylthioxanthone,diethylthioxanthone, dimethylthioxanthone and the like.

Other Initiators

Benzyl, α-acyloxime ester, acylphosphine oxide, glyoxyester,3-ketocoumaran, 2-ethylanthraquinone, camphorquinone, anthraquinone andthe like.

Depending on kind of the fluorine-containing polymer or kind of theabove-mentioned active energy curing initiator, there is a case wherecompatibility between the polymer and the initiator is not good and thecoating composition itself or a coating film after coating becomesturbid in white and transparency and curing reactivity are lowered(Experimental Example 21(1)).

The present inventors have found that compatibility between the polymerand the initiator can be improved by introducing fluorine atom or anorganic group having fluorine atom to the active energy curinginitiator.

Concretely preferred are initiators having a fluorine-containing alkylgroup, a fluorine-containing alkylene group, a fluorine-containing alkylgroup having ether bond or a fluorine-containing alkylene group havingether bond. For example, there are an initiator in which afluorine-containing carboxylic acid (polycarboxylic acid) or the likehaving the above-mentioned fluorine-containing organic group isintroduced into an initiator having OH group by ester bonding(Experimental Example 18) and an initiator in which afluorine-containing carboxylic acid (polycarboxylic acid) or the like isintroduced into an initiator having amino group by amide bonding.

The introduction of the fluorine-containing organic group to theinitiator is preferred since even in the fluorine-containing polymerhaving a high fluorine content, compatibility is good and curingreactivity and transparency of the coating film can be improved(Experimental Example 21(1)).

Also as case demands, an auxiliary for photo-initiation such as amines,sulfones or sulfines may be added.

Also examples of the initiator which initiates curing of the curablefluorine-containing polymer (a) having a cation-reactive carbon-carbondouble bond are those mentioned below.

Onium Salts

Iodonium salt, sulfonium salt, phosphonium salt, diazonium salt,ammonium salt, pyridinium salt and the like.

Sulfone Compounds

β-ketoester, β-sulfonylsulfone, α-diazo compounds thereof and the like.

Sulfonic Acid Esters

Alkylsulfonic acid ester, haloalkylsulfonic acid ester, arylsulfonicacid ester, iminosulfonate and the like.

Others

Sulfone imide compounds, diazomethane compounds and the like.

Also in those cation-reactive active energy curing initiators,compatibility thereof with the fluorine-containing polymer can beimproved by introducing fluorine atom or a fluorine-containing organicgroup to the initiators like the above-mentioned case.

Another embodiment of the curable fluorine-containing resin compositionof the present invention is one using a solvent, which is preferablefrom the point that the composition dissolved and dispersed in thesolvent can be coated on various substrates to form a coating film andthe coating film can be effectively cured by irradiation with activeenergy or the like to obtain a cured coating film.

Namely, the fluorine-containing resin composition for coating of thepresent invention is the composition comprising:

(a) a curable fluorine-containing polymer,(b) an active energy curing initiator and(c) a solvent.

There can be preferably used the same curable fluorine-containingpolymer (a) and active energy curing initiator (b) as in theabove-mentioned curable fluorine-containing resin composition.

The solvent (c) is not limited particularly as far as the curablefluorine-containing polymer (a), active energy curing initiator (b) andadditives such as a curing agent, leveling agent and light-stabilizer tobe added as case demands are uniformly dissolved and dispersed therein.Particularly preferred is the solvent which uniformly dissolves thecurable fluorine-containing polymer (a). This embodiment using thesolvent is preferable from the point that a coating film having a hightransparency and uniformity can be obtained in high productivityparticularly in the antireflection film application, etc. where a thincoating film (about 0.1 μm thick) is required.

Examples of the solvent (c) are, for instance, cellosolve solvents suchas methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate andethyl cellosolve acetate; ester solvents such as diethyl oxalate, ethylpyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate,amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyllactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; propylene glycolsolvents such as propylene glycol monomethyl ether, propylene glycolmonoethyl ether, propylene glycol monobutyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,propylene glycol monobutyl ether acetate and dipropylene glycol dimethylether; ketone solvents such as 2-hexanone, cyclohexanone, methyl aminoketone and 2-heptanone; alcohol solvents such as methanol, ethanol,propanol, isopropanol and butanol; aromatic hydrocarbons such as tolueneand xylene; a solvent mixture of two or more thereof and the like.

Also in order to enhance solubility of the curable fluorine-containingpolymer (a), a fluorine-containing solvent may be used as case demands.

Examples of the fluorine-containing solvent are, for instance, CH₃CCl₂F(HCFC-141b), a mixture of CF₃CF₂CHCl₂ and CClF₂CF₂CHClF (HCFC-225),perfluorohexane, perfluoro(2-butyltetrahydrofuran),methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, and inaddition, fluorine-containing alcohols such as:

H(CF₂CF₂_(n)CH₂OH (n: an integer of from 1 to 3),

F(CF₂_(n)CH₂OH (n: an integer of from 1 to 5) and

(CF₃₂CHOH,

benzotrifluoride, perfluorobenzene, perfluoro(tributylamine),ClCF₂CFClCF₂CFCl₂ and the like.

Those fluorine-containing solvents may be used solely, in a mixture oftwo or more thereof or in a mixture of one or more of thefluorine-containing solvents and non-fluorine-containing solvents.

Among them, ketone solvents, acetic acid ester solvents, alcoholsolvents and aromatic solvents are preferred from the viewpoint ofcoatability and productivity of a coating film.

The present inventors have found that at dissolving the curablefluorine-containing polymer, when the fluorine-containing alcoholsolvent is mixed to the above-mentioned general-purpose solvent, aleveling property of the polymer coating film after the coating on asubstrate and drying can be improved.

This effect of improving a leveling property is high in the case ofresin substrates, particularly an acrylic resin, cellulose resin,polyethylene terephthalate, polycarbonate and polyolefin and isexhibited significantly particularly in the case of a polyethyleneterephthalate substrate (Experimental Examples 44 and 45).

The fluorine-containing alcohol to be added may be one which has aboiling point of not less than 50° C., preferably not less than 80° C.and dissolves the curable fluorine-containing polymer.

Examples thereof are, for instance,

HCF₂CF₂_(n)CH₂OH (n is an integer of from 1 to 4),

FCF₂_(n)CH₂OH (n is an integer of from 1 to 6),

(CF₃₂CHOH

and the like.

Though the fluorine-containing alcohol may be used solely as a solvent,it is effective to mix the fluorine-containing alcohol in addition tothe above-mentioned general purpose solvent such as ketone solvent,acetic acid ester solvent, non-fluorine-containing alcohol solvent,aromatic solvent or the like.

When the fluorine-containing alcohol is mixed, an adding amount thereofis not less than 1% by weight, preferably not less than 5% by weight,more preferably not less than 10% by weight, particularly from 10% byweight to 30% by weight based on the whole solvents.

Further in the present invention, as case demands, a curing agent may beadded to the curable fluorine-containing resin composition comprisingthe curable fluorine-containing polymer (a) and the active energy curinginitiator (b) and also to the fluorine-containing resin composition forcoating further containing the solvent (c).

Preferred curing agents are those which have at least one carbon-carbonunsaturated bond and can be polymerized with radical or an acid.Examples thereof are concretely radically polymerizable monomers such asan acrylic monomer and cationically polymerizable monomers such as avinyl ether monomer. Those monomers may be monofunctional monomershaving one carbon-carbon double bond or polyfunctional monomers havingtwo or more carbon-carbon double bonds.

Those so-called curing agents having a carbon-carbon unsaturated bondreact by radical or cation generated by reaction of the active energycuring initiator (b) in the composition of the present invention withthe active energy such as light and can be crosslinked with thecarbon-carbon double bond in the side chain of the curablefluorine-containing polymer (a) in the composition of the presentinvention by copolymerization.

Examples of the monofunctional acrylic monomer are acrylic acid, acrylicacid esters, methacrylic acid, methacrylic acid esters, α-fluoroacrylicacid, α-fluoroacrylic acid esters, maleic acid, maleic anhydride, maleicacid esters and (meth)acrylic acid esters having epoxy, hydroxyl,carboxyl or the like.

Among them, preferred are acrylate monomers having a fluoroalkyl groupto maintain a low refractive index of the cured article. For example,preferred are compounds represented by the formula:

wherein X is H, CH₃ or F; Rf is a fluorine-containing alkyl group having2 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to100 carbon atoms and ether bond.

Examples thereof are:

(n: from 1 to 5) and the like.

As the polyfunctional acrylic monomer, there are generally knowncompounds obtained by replacing hydroxyl groups of polyhydric alcoholssuch as diol, triol and tetraol with acrylate groups, methacrylategroups or α-fluoroacrylate groups.

Examples thereof are compounds obtained by replacing two or morehydroxyl groups of polyhydric alcohols such as 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol,neopentyl glycol, trimethylol propane, pentaerythritol anddipentaerythritol with any of acrylate groups, methacrylate groups orα-fluoroacrylate groups.

Also there can be used polyfunctional acrylic monomers obtained byreplacing two or more hydroxyl groups of polyhydric alcohols having afluorine-containing alkyl group, a fluorine-containing alkyl grouphaving ether bond, a fluorine-containing alkylene group or afluorine-containing alkylene group having ether bond with acrylategroups, methacrylate groups or α-fluoroacrylate groups. Those monomersare preferred particularly from the point that a low refractive index ofthe cured article can be maintained.

Preferable examples thereof are compounds having structures obtained byreplacing two or more hydroxyl groups of fluorine-containing polyhydricalcohols represented by the formulae:

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms)

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms ora fluorine-containing alkyl group having 1 to 40 carbon atoms and etherbond, R is H or an alkyl group having 1 to 3 carbon atoms)

(Rf′ is a fluorine-containing alkylene group having 1 to 40 carbon atomsor a fluorine-containing alkylene group having 1 to 40 carbon atoms andether bond, R is H or an alkyl group having 1 to 3 carbon atoms) withacrylate groups, methacrylate groups or α-fluoroacrylate groups.

When those exemplified monofunctional and polyfunctional acrylicmonomers are used as the curing agent for the composition of the presentinvention, particularly preferred are α-fluoroacrylate compounds fromthe viewpoint of good curing reactivity.

In the composition of the present invention, an adding amount of theactive energy curing initiator (b) is optionally selected depending onthe content of the carbon-carbon double bonds in the curablefluorine-containing polymer (a), an amount of the curing agent andfurther kinds of the initiator and active energy and an amount ofirradiation energy (intensity and time) and also depending on whether ornot the above-mentioned curing agent is used. When the curing agent isnot used, the amount of the initiator is from 0.01 to 30 parts byweight, preferably from 0.05 to 20 parts by weight, most preferably from0.1 to 10 parts by weight based on 100 parts by weight of the curablefluorine-containing polymer (a).

Concretely the amount of the initiator is from 0.05 to 50% by mole,preferably from 0.1 to 20% by mole, most preferably from 0.5 to 10% bymole based on the content (the number of moles) of the carbon-carbondouble bonds contained in the curable fluorine-containing polymer (a).

When the curing agent is used, the amount of the initiator is from 0.05to 50% by mole, preferably from 0.1 to 20% by mole, most preferably from0.5 to 10% by mole based on the total number of moles including thecontent (number of moles) of the carbon-carbon double bonds contained inthe curable fluorine-containing polymer (a) and the number of moles ofthe carbon-carbon unsaturated bonds of the curing agent.

When the curing agent is used, the amount of the curing agent isoptionally selected depending on intended hardness and refractive index,kind of the curing agent, the content of curable groups of the curablefluorine-containing polymer, etc. The amount is desirably from 1 to 80%by weight, preferably from 5 to 70% by weight, more preferably from 10to 50% by weight based on the curable fluorine-containing polymer. Ifthe amount of the curing agent is too large, there is a tendency thatthe refractive index is increased, which is not preferable.

The content of the solvent (c) in the fluorine-containing resincomposition for coating of the present invention is optionally selecteddepending on kinds of solids to be dissolved, the amount of the curingagent, kind of a substrate, intended coating thickness, etc. and alsodepending on whether or not the curing agent is used. It is preferableto decide the amount of the solvent so that a concentration of the wholesolids in the composition becomes from 0.5 to 70% by weight, preferablyfrom 1 to 50% by weight.

To the composition of the present invention may be added variousadditives as case demands in addition to the above-mentioned compounds.

Examples of the additives are, for instance, a leveling agent, viscositycontrol agent, light-stabilizer, moisture absorbing agent, pigment, dye,reinforcing agent and the like.

Also to the composition of the present invention can be added fineparticles of inorganic compounds to increase hardness of the curedarticle.

The fine particles of inorganic compound are not limited particularly.Preferred are compounds having a refractive index of not more than 1.5.Desirable fine particles are magnesium fluoride (refractive index:1.38), silicon oxide (refractive index: 1.46), aluminum fluoride(refractive index: from 1.33 to 1.39), calcium fluoride (refractiveindex: 1.44), lithium fluoride (refractive index: from 1.36 to 1.37),sodium fluoride (refractive index: from 1.32 to 1.34), thorium fluoride(refractive index: from 1.45 to 1.50) and the like. It is desirable thata particle size of the fine particles is sufficiently small as comparedwith wavelengths of visible light in order to ensure transparency of thelow refractive index material. The particle size is preferably not morethan 100 nm, particularly preferably not more than 50 nm.

When the fine particles of inorganic compound are used, it is desirableto use them in the form of organic sol previously dispersed in anorganic dispersion in order not to lower dispersion stability in thecomposition and adhesion in the low refractive index material. Furtherin order to enhance dispersion stability of the fine particles ofinorganic compound in the composition and adhesion in the low refractiveindex material, surfaces of the fine particles of inorganic compound canbe previously modified with various coupling agents. Examples of thecoupling agent are, for instance, organosilicon compounds; metalalkoxides such as aluminum, titanium, zirconium, antimony and a mixturethereof; salts of organic acids; coordination compounds bonded with acoordinative compound; and the like.

In the fluorine-containing resin composition for coating of the presentinvention, the curable fluorine-containing polymer (a) or additives maybe in either form of dispersion or solution in the solvent (c). In orderto form a uniform thin coating film and enable the coating film to beformed at relatively low temperatures, the form of uniform solution ispreferred.

For the coating, known coating methods can be employed as far as acoating thickness can be controlled.

For example, there can be employed a roll coating method, gravurecoating method, micro-gravure coating method, flow coating method, barcoating method, spray coating method, dye coating method, spin coatingmethod, dip coating method and the like. The coating method can beselected in consideration of kind and shape of a substrate,productivity, controllability of a coating thickness, etc.

The curable resin composition of the present invention comprising thecurable fluorine-containing polymer (a) and the active energy curinginitiator (b) and the coating film obtained by coating thefluorine-containing resin composition for coating of the presentinvention on a substrate by the above-mentioned coating method and thendrying can be photo-cured by irradiation of active energy rays such asultraviolet light, electron beam or radioactive ray.

By the photo-curing, the carbon-carbon double bonds in the curablefluorine-containing polymer (a) of the present invention are polymerizedbetween the molecules, and the carbon-carbon double bonds in the polymerdecrease or disappear. As a result, hardness of the resin becomes high,a mechanical strength is increased, abrasion resistance and scratchresistance are increased and further the composition not only becomesinsoluble in a solvent in which the composition is soluble before thecuring but also becomes insoluble in many other kinds of solvents.

The fourth of the present invention relates to the antireflection film.

Namely, the antireflection film is the cured coating film of thefluorine-containing prepolymer which has a coating thickness of from0.03 to 0.5 μm and is characterized in that the prepolymer has:

(1) a carbon-carbon unsaturated bond at an end of its side chain, and(2) a refractive index of not more than 1.40.

This invention was completed based on the findings of the presentinventors that when the fluorine-containing prepolymer which has acarbon-carbon unsaturated bond capable of curing (crosslinking) and islow in a refractive index is coated on a transparent substrate in aspecific coating thickness and is cured, an antireflection film having areflection reducing effect and in addition, a high hardness, abrasionresistance and scratch resistance can be obtained. When such aprepolymer is used, coatability (smoothness and uniformity of a coatingthickness) is good, a low molecular weight monomer component is hard toremain in the coating film after the curing, and therefore the coatingfilm is free from feeling of tackiness on its surface and has excellentcharacteristics.

The curing can be carried out with heat and light (in a systemcontaining an initiator). However when the antireflection film isprovided on a transparent resin substrate, applying high temperatures onthe substrate is not preferable because thermal deterioration andthermal deformation of the substrate are apt to occur. Therefore thecuring with light is preferred, and it is preferable that thefluorine-containing prepolymer has a carbon-carbon unsaturated bondcapable of photo-curing (for example, photo-polymerizing).

For obtaining an antireflection film by photo-curing afluorine-containing prepolymer, there is usually employed a method ofobtaining a cured coating film by preparing a coating compositioncomprising:

(d) the above-mentioned fluorine-containing prepolymer,(e) an active energy curing initiator, and(f) a solvent,coating the coating composition on a substrate, forming a coating film(not-cured) by drying and then irradiating the coating film with activeenergy ray such as ultraviolet light, electron beam, radioactive ray orthe like. The light irradiation may be carried out in either of airstream and inert gas stream such as nitrogen gas. Particularly the lightirradiation in an inert gas stream is preferred from the viewpoint ofgood curing reactivity, and a coating film having a higher hardness canbe obtained.

As the fluorine-containing prepolymer (d) for the antireflection film ofthe present invention, any of fluorine-containing prepolymers can beused as far as they have a reactive carbon-carbon unsaturated bond inthe side chain thereof. From the viewpoint of good reactivity, anethylenic carbon-carbon double bond is preferred.

Particularly preferred is a combination use of the fluorine-containingprepolymer (d1) having a radically polymerizable ethylenic carbon-carbondouble bond and the initiator (e) generating radical by irradiation ofactive energy ray from the point that the polymerization reaction occursrapidly, a degree of polymerization is high and the curing can be easilycarried out.

Also the fluorine-containing prepolymer (d2) having anacid-polymerizable carbon-carbon double bond can be used in combinationwith an initiator generating an acid by irradiation of active energyray, which is preferable from the point that the curing reaction is lessaffected by air (oxygen), etc. at the time of light irradiation.

The fluorine-containing prepolymer to be used for the antireflectionfilm of the present invention is preferably the same as theabove-mentioned curable fluorine-containing polymers, and among theabove-mentioned examples of the curable polymer, those which have a hightransparency, are non-crystalline and have a refractive index of notmore than 1.40, preferably not more than 1.38 are selected. Furtheramong them, it is preferable to optionally select the polymers dependingon intended hardness, kind of a substrate, coating method, coatingconditions, coating thickness, uniformity of a coating film, adhesion tothe substrate, etc.

As the active energy curing initiator (e) to be used for theantireflection film of the present invention, the same initiators asexemplified in the above-mentioned curable fluorine-containing resincomposition can be used. Kind and an amount of the initiator can beoptionally selected in the above-mentioned range in consideration ofkind (reactivity, content) of the carbon-carbon unsaturated bond in thefluorine-containing prepolymer, curing conditions, a pot life of thecoating, etc.

As the solvent (f), there can be used those exemplified in theabove-mentioned curable resin composition for coating. Kind and anamount of the solvent (f) are optionally selected from theabove-mentioned examples depending on intended coatability, film formingproperty, uniformity of a coating thickness, productivity in coating,etc. Among the solvents, those which cause dissolving and swelling ofthe transparent substrate are not preferred.

Particularly preferred are those selected from ketone solvents, aceticacid ester solvents, alcohol solvents and aromatic hydrocarbon solvents.

In the antireflection film of the present invention, it is natural thatthe same curing agent (g) as mentioned above may be used together withthe curable fluorine-containing prepolymer (d). The use of the curingagent can make hardness of the cured coating film higher.

Kind and an amount of the curing agent (g) to be used preferably are thesame as those mentioned in the above-mentioned fluorine-containing resincomposition for coating.

It is preferable that after coating of the coating composition andcuring of the fluorine-containing prepolymer, the cured article (coatingfilm) has a refractive index of not more than 1.49, more preferably notmore than 1.45, further preferably not more than 1.40. Most preferred isa refractive index of not more than 1.38. A lower refractive index ismore advantageous from the viewpoint of a reflection reducing effect.

A preferable coating thickness of the antireflection film to be used onvarious substrates varies with the refractive indices of the film andsubstrate and is selected in the range of from 0.03 to 0.5 μm,preferably from 0.07 to 0.2 μm, more preferably from 0.08 to 0.12 μm.When the coating thickness is too small, there is a tendency thatreduction of reflectance due to light interference in visible lightbecomes insufficient. When the coating thickness is too large, since thereflectance comes to depend only on a reflection nearly at an interfacebetween air and film, there is a tendency that reduction of reflectancedue to light interference in visible light becomes insufficient. It isparticularly preferable that a proper coating thickness is set so that awavelength exhibiting a minimum reflectance of an antireflection-treatedarticle provided with the antireflection film is usually from 420 to 720nm, preferably from 520 to 620 nm.

The fifth of the present invention relates to the antireflection-treatedarticle obtained by applying the antireflection film on a substrate.

Kind of the article, namely kind of the substrate which is provided withthe antireflection film is not limited particularly. Examples thereofare, for instance, inorganic materials such as glass, stone, concreteand tile; synthetic resins, namely vinyl chloride resin, polyethyleneterephthalate, cellulose resins such as triacetyl cellulose,polycarbonate resin, polyolefin resin, acrylic resin, phenol resin,xylene resin, urea resin, melamine resin, diallyl phthalate resin, furanresin, amino resin, alkyd resin, urethane resin, vinyl ester resin andpolyimide resin; metals such as iron, aluminum and copper; wood, paper,printed matter, printing paper, picture, etc. When a certain portion ofthe article other than a specific portion thereof is provided with theantireflection film and the shape of the specific portion is lifted upby a reflecting light, a decorative effect of the article can beenhanced.

The antireflection film can be preferably provided particularly on thetransparent resin substrates such as an acrylic resin, polycarbonate,cellulose rein, polyethylene terephthalate and polyolefin resin, and areflection reducing effect can be exhibited effectively.

The present invention is effectively applied on the following articles.

Optical parts such as prism, lens sheet, polarizing plate, opticalfilter, lenticular lens, Fresnel lens, screen of rear projectiondisplay, optical fiber and optical coupler;Transparent protection plates represented by glass for show window,glass for display case, cover for advertisement and cover forphoto-stand;Protection plates for CRT, liquid crystal display, plasma display andrear projection display;Optical recording media such as magnetic optical disk, read only typeoptical disks such as CD, LD and DVD, phase transition type optical disksuch as PD and hologram recorder;Photolithography-related members for production of semiconductors suchas photoresist, photomask, pellicle and reticule;Protection covers for light emitters such as halogen lamp, fluorescentlamp and incandescent lamp; andSheet or film for adhering to the above-mentioned articles.

The antireflection film of the present invention may be formed into acured coating film having a thickness of about 0.1 μm by applying asolution of the fluorine-containing prepolymer (d) directly on asubstrate and then irradiating the coating film with light, or theantireflection film may be formed, as a top coat, on one or pluralundercoat layers formed on the substrate.

The effects of the undercoat are roughly classified into three, namelyan increase of scratch resistance of the top coat, protection of thesubstrate and an increase of a reflection reducing effect by providingthe layers having a refractive index higher than that of the substrate.In order to increase scratch resistance of the top coat, aself-repairing undercoat mentioned in JP7-168005A may be used. Also forthe protection of the substrate, a coating generally called a hard coatmay be used. Examples of the hard coat are cured articles from curableacrylic resin, epoxy resin and silicon alkoxide compounds, curedarticles from metal alkoxide compounds and the like. A heat curingmethod can be applied on all of them. For the acrylic resin and epoxyresin, a photo-curing method (ultraviolet light) is preferred from theviewpoint of productivity.

With respect to CRT and plasma display, static electricity easilydeposits on the surface thereof due to characteristics of equipment.Therefore it is preferable to mix, to the undercoat layer and/or topcoat layer as mentioned above, an additive imparting electricconductivity. Examples of the additive are polymers having ionic groupsuch as —COO—, —NH₂, —NH₃ ⁺, —NR¹¹R¹²R¹³, in which R¹¹, R¹² and R¹³ are,for example, methyl, ethyl, n-propyl, n-butyl or the like, or —SO₃—,silicone compounds, inorganic electrolytes (for example, NaF, CaF₂,etc.) and the like.

Also in order to prevent adhesion of dust, it is preferable to add ananti-static agent to the undercoat layer of the antireflection filmand/or top coat layer. Examples of the additive are the above-mentionedadditives imparting electric conductivity and in addition, fineparticles of metal oxides, fluoroalkoxysilane, surfactants (anionic,cationic, amphorytic and nonionic surfactants) and the like.

Examples of the preferable anti-static agent to be added to theundercoat layer are fine particles of metal oxides, concretelyantimony-doped tin oxide (ATO) and indium-containing tin oxide (ITO)since the anti-static effect is high, is maintained for a long period oftime and is hardly affected by humid and since the refractive index ofthe substrate can be adjusted because transparency and refractive indexof the anti-static agent are high, thereby enabling the reflectionreducing effect to be enhanced. From the viewpoint of transparency, ATOis preferred, and from the viewpoint of anti-static effect or electricconductivity, ITO is preferred. Even in case where no anti-static effectis required, a reflection reducing effect can be increased with thoseadditives since the refractive index can be adjusted easily.

Also since ATO and ITO easily scatter and absorb light, in order not toprevent transmission of light, the thickness of the undercoat layer ispreferably sub-micron or so. In order to decrease dependency of thereflection reducing effect on a wavelength and to increase thereflection reducing effect throughout the whole wavelength, thethickness of the undercoat layer is preferably from 0.05 to 0.3 μmthough it depends on the refractive index of the curedfluorine-containing prepolymer. An optimum refractive index ispreferably from 1.55 to 1.95 though it also depends on the refractiveindex of the fluorine-containing polymer.

In order to impart anti-static property to the cured fluorine-containingprepolymer coating film, alkoxysilane anti-static agents are preferredfrom the point that the refractive index is hardly increased and thoseagents do not have an adverse effect on the reflection reducing effect.Fluoroalkoxysilane is further preferred since its action to increase therefractive index is further smaller and in addition, an effect ofimproving surface characteristics can be expected.

Also as a method entirely different from the above-mentioned method ofmodifying a part of the film, there is a method of forming a surfactantlayer in a thickness not having an adverse effect on the reflectionreducing ability as mentioned in JP8-142280A. When this method isapplied to the present invention, there is an effect of preventingadhesion of dust and enhancing stain-proofing property. There is thesame effect also in the case of forming the hard coat layer.

The hard coat layer can be formed by the method of coating a solution ofalkoxysilane or polysilazane and then heating and curing. Also a curedfilm obtained from an ultraviolet curable acrylic coating or a curedfilm obtained by melamine-crosslinking can be used.

Further the antireflection film of the present invention may be providedon an undercoat layer formed by applying a coating agent containing fineparticles as a flattening agent, namely on a substrate film (forexample, TAC film and the like) subjected to anti-glaring (AG)treatment. Thereby the antireflection film having a low gloss and a lowreflection can be obtained. Such a film, when used for LCD and the like,is preferred since a further vivid image can be obtained.

The antireflection film of the present invention has a high fluorinecontent and a low surface contact angle and also possesses waterrepelling property, non-tackiness and stain-proofing property andtherefore can be used as both of the antireflection layer andstain-proofing layer.

Further in order to impart stain-proofing property to the antireflectionlayer, a fluorine-containing polyether compound can be added. In thatcase, the adding amount of the compound need be decided in considerationof lowering of mechanical properties and white turbidity due to phaseseparation from the fluorine-containing polymer. When carboxyl group,blocked carboxyl group, hydroxyl group, epoxy group, alkoxysilane group,(meth)acryloyl group or α-fluoroacryloyl group is introduced to an endof the compound, the compound is easily fixed in the coating film(Experimental Examples 33, 34 and 35). Also there is the same effectwhen the same polyether compound as above is coated on a surface of apreviously formed antireflection film (a coating film before or aftercuring).

For forming a thin film of the curable fluorine-containing polymer,there are a method of coating a dispersion of the curablefluorine-containing polymer, drying and then baking if necessary and amethod of coating a solution (uniform solution) of the polymer and thendrying. Preferred is the coating of the solution since a thin film iseasily formed. In that case, as far as a coating thickness can becontrolled sufficiently, known coating methods can be employed. Forexample, a roll coating method, micro gravure coating method, gravurecoating method, flow coating method, bar coating method, spray coatingmethod, die coating method, spin coating method and dip coating methodcan be employed. The optimum coating method is selected from them inconsideration of a balance of productivity, controllability of a coatingthickness, yield, etc. The antireflection film formed into a film orsheet may be adhered to a substrate.

In the present invention, a silane compound may be added to enhanceadhesion of the antireflection film to the substrate. An amount of thesilane compound added to the coating film may be several % by weight.Also treating of a substrate surface with a silane compound has aneffect on improvement of adhesion. In the present invention, in any ofthe above cases, the silane compound hardly increases the refractiveindex of the cured film and therefore an influence thereof on thereflection reducing effect is very small.

The present invention is then explained by means of experimentalexamples, but is not limited to them.

Preparation Example 1 Synthesis of Homopolymer of Fluorine-ContainingAllyl Ether Having OH Group

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 20.4 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol):

and 21.2 g of a perfluorohexane solution of 8.0% by weight of:

[HCF₂CF₂₃COO₂

and after the inside of the flask was sufficiently replaced withnitrogen gas, stirring was carried out at 20° C. for 24 hours innitrogen gas stream and thereby a solid having a high viscosity wasproduced.

The obtained solid was dissolved in diethyl ether and poured intoperfluorohexane, followed by separating and vacuum drying to obtain 17.6g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 9,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was22,000.

Experimental Example 1 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 80 ml ofdiethyl ether, 5.0 g of the fluorine-containing allyl ether homopolymerhaving hydroxyl which was obtained in Preparation Example 1 and 1.0 g ofpyridine, followed by cooling to 5° C. or lower with ice.

Then a solution obtained by dissolving 1.0 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 20 ml of diethyl ether was added thereto dropwiseover about 30 minutes while stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 4.0 hours.

The ether solution after the reaction was put in the dropping funnel,followed by washing with water, 2% hydrochloric acid solution, 5% NaClsolution and water and then drying with anhydrous magnesium sulfate.Then the ether solution was separated by filtration.

According to ¹⁹F-NMR analysis of the ether solution, the obtainedpolymer was a copolymer comprising a fluorine-containing allyl etherhaving

group and a fluorine-containing allyl ether having OH group in a ratioof 40:60% by mole.

The ether solution was coated on a NaCl plate and formed into a castfilm at room temperature. According to IR analysis of the cast film, anabsorption of a carbon-carbon double bond was observed at 1,661 cm⁻¹,and an absorption of C═O group was observed at 1,770 cm⁻¹.

Experimental Example 2 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A curable fluorine-containing polymer (ether solution) was synthesizedin the same manner as in Experimental Example 1 except that 0.65 g ofα-fluoroacrylic acid fluoride CH₂═CFCOF and 1.0 g of pyridine were used.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having

group and a fluorine-containing allyl ether having OH group in a ratioof 30:70% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 1.

Experimental Example 3 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A curable fluorine-containing polymer (ether solution) was synthesizedin the same manner as in Experimental Example 1 except that 0.35 g ofα-fluoroacrylic acid fluoride CH═CFCOF and 0.3 g of pyridine were used.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having

group and a fluorine-containing allyl ether having OH group in a ratioof 15:85% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 1.

Experimental Example 4 (1) Preparation of Fluorine-Containing ResinComposition for Coating

After methyl ethyl ketone (MEK) was added to the fluorine-containingpolymer (ether solution) having α-fluoroacryloyl group which wasobtained in Experimental Example 1, ether was distilled off with anevaporator to adjust a concentration of the polymer to 8.0% by weight.

To 10 g of the obtained polymer solution was added, as an active energycuring initiator, 1.7 g of a solution obtained by dissolving2-hydroxy-2-methyl propiophenone in MEK in a concentration of 1% byweight.

(2) Production of Antireflection Film

The above-mentioned coating composition was coated on a non-treatedacryl plate at room temperature at 1,000 to 2,000 rpm with a spincoater, followed by drying at 50° C. for five minutes. The number ofrevolutions of the spin coater was adjusted so that a coating thicknessafter the drying became from 90 to 110 nm.

(Light Irradiation)

The coating film after the drying was irradiated with ultraviolet lightat an intensity of 3,000 mJ/cm²U using a high pressure mercury lamp.

(3) Measurement of Refractive Index of Curable Fluorine-ContainingPolymer

The 8% MEK solution of the curable fluorine-containing polymer (thepolymer solution before adding the catalyst for curing in (1) above) wascoated on a PET film with an applicator so that a coating thicknessafter the drying became about 100 μm. After drying at 50° C. for tenminutes, the obtained cast film was peeled from the PET film and arefractive index thereof was measured using an Abbe's refractometer at25° C. with light having a wavelength of 550 nm. The results are shownin Table 1.

(4) Measurement of Refractive Index of Cured Film

The coating composition prepared in (1) above was coated on an aluminumfoil with an applicator so that a coating thickness became about 100 μm,followed by drying at 50° C. for ten minutes. After the lightirradiation was carried out in the same manner as in (2) above, thealuminum foil was melted with diluted hydrochloric acid to obtain asample film. A refractive index of the obtained cured film was measuredin the same manner as in (3) above.

(5) Measurement of Reflectance of One Side of Film

The acryl plate having the antireflection film which was obtained in (2)above was set on a UV-VIS spectrophotometer equipped with a 5° regularreflection unit, and a reflectance was measured with light having awavelength of 550 nm.

(6) Evaluation of Physical Properties of Antireflection Film

The following physical properties of the antireflection film obtained in(2) above were evaluated.

{circle around (1)} Set to Touch

Tackiness of the film is evaluated by touching with a finger accordingto JIS K4500.

The evaluation is made as follows.◯: There is no tackiness.x: There is tackiness.{circle around (2)} Pencil Hardness

Measured according to JIS K5400.

{circle around (3)} Solvent Resistance

After the surface of the coating film is rubbed with a cotton clothimpregnated with ethyl acetate, condition (dissolved or peeled) of thesurface is evaluated.

When there is no change, it is evaluated as ◯, and when there isdissolving or peeling, it is evaluated as x.

The evaluation is also carried out in the same manner as above withrespect to the case using acetone as a solvent.

{circle around (4)} Abrasion Resistance

A cotton cloth (BEMCOT (Registered trademark) M-3 available from AsahiChemical Co., Ltd.) is fitted to a rubbing tester, and theantireflection film is rubbed by 100 rubbing cycles at a load of 100gf/cm². Then the condition of the film is observed.

The evaluation is made as follows.

◯: There is no change.Δ: A flaw is found partly.x: There is a portion where a film is peeled and a substrate is seen.

Experimental Examples 5 to 6

Preparation of a coating composition, production of an antireflectionfilm and evaluation of a coating film were carried out in the samemanner as in Experimental Example 4 except that the fluorine-containingpolymers of Experimental Example 2 (Experimental Example 5) andExperimental Example 3 (Experimental Example 6) were used instead of thefluorine-containing polymer having α-fluoroacryloyl group which wasobtained in Experimental Example 1. The results are shown in Table 1.

Experimental Example 7

An antireflection film was produced in the same manner as inExperimental Example 4 except that light irradiation was not conductedin producing the antireflection film, and evaluation of physicalproperties was made. The results are shown in Table 1.

Experimental Example 8

A reflectance of one side of a non-coated acryl plate was measured. Theresults are shown in Table 1.

TABLE 1 Experimental Example 4 5 6 7 8 Substrate film Acryl Acryl AcrylAcryl Acryl Curable fluorine-containing Exp. Ex. 1 Exp. Ex. 2 Exp. Ex. 3Exp. Ex. 1 polymer Content of —O(C═O)CF═CH₂ 40 30 15 40 group (% bymole) Solvent MEK MEK MEK MEK Concentration of polymer 8.0 8.0 8.0 8.0Non-coated (% by weight) Active energy curing agent 2-hydroxy-2-2-hydroxy-2- 2-hydroxy-2- 2-hydroxy-2- methyl- methyl- methyl- methyl-propiophenone propiophenone propiophenone propiophenone Proportion topolymer 2.1 2.1 2.1 2.1 (% by weight) Amount of ultraviolet 3,000 3,0003,000 Not irradiated irradiation (mJ/cm²) Refractive index Non-coatedBefore curing 1.362 1.359 1.356 — After curing 1.366 1.364 1.361 —Reflectance of one side of 1.3 1.2 1.0 — 4.0 film (%) Set to touch ∘ ∘ ∘x Non-coated Pencil hardness 2H 2H H B Solvent resistance ∘ ∘ ∘ xAbrasion resistance ∘ ∘ ∘ x

Experimental Examples 9 to 12 Determination of Curing Reactivity by IRAnalysis (1) Preparation of Fluorine-Containing Resin Composition forCoating

Respective coating compositions were prepared using the curablefluorine-containing polymer obtained in Experimental Example 1 by thesame procedures as in Experimental Example 4 so that the concentrationsof the polymer and the amounts of active energy curing initiator becamethose shown in Table 2.

(2) Production of Film for IR Analysis

The coating compositions prepared in (1) above were coated on a PET filmwith an applicator so that a coating thickness after drying became about100 μm, followed by drying at 50° C. for five minutes. Then the obtainedcoating films were peeled from the PET film to obtain cast films.

(3) Measurement of Curing Reactivity by IR Analysis

According to IR analysis of the cast films, an absorption of acarbon-carbon double bond in the polymer was observed at 1,661 cm⁻¹.

Attention was directed to this absorption of the carbon-carbon doublebond, and a change in an intensity of absorption after the lightirradiation was measured. A ratio of curing reaction was measured by thefollowing equation.

$\left( {1 - \frac{{Peak}\mspace{14mu} {height}\mspace{14mu} {at}\mspace{14mu} 1,661\mspace{14mu} {cm}^{- 1}\mspace{14mu} {after}\mspace{14mu} {light}\mspace{14mu} {irradiation}}{{Peak}\mspace{14mu} {height}\mspace{14mu} {at}\mspace{14mu} 1,661\mspace{14mu} {cm}^{- 1}\mspace{14mu} {before}\mspace{14mu} {light}\mspace{14mu} {irradiation}}} \right) \times 100\%$

The films were irradiated with ultraviolet light at room temperature inirradiation amounts shown in Table 2 using a high pressure mercury lamp.The amount of irradiation was changed and the ratio of curing reactionrepresented by the above equation was calculated. The results are shownin Table 2.

TABLE 2 Experimental Example 9 10 11 12 Curable fluorine-containing Exp.Ex. 1 Exp. Ex. 1 Exp. Ex. 1 Exp. Ex. 1 polymer Content of —O(C═O)CF═CH₂group 40 40 40 40 (% by mole) Solvent MEK MEK MEK MEK Concentration ofpolymer 8 8 8 8 (% by weight) Active energy curing initiator2-hydroxy-2- 2-hydroxy-2- 2-hydroxy-2- 2-hydroxy-2- methyl- methyl-methyl- methyl- propiophenone propiophenone propiophenone propiophenoneProportion to polymer 4.2 2.1 1.0 0.2 (% by weight) Ratio of curingreaction (%) Amount of ultraviolet irradiation (mJ/cm²)   100 100 60 4534 (disappeared)   500 — 82 60 44 1,500 — 100 74 55 (disappeared)

Experimental Example 13 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A curable fluorine-containing polymer (ether solution) was synthesizedin the same manner as in Experimental Example 1 except that 2.0 g ofα-fluoroacrylic acid fluoride (CH₂═CFCOF) and 2.0 g of pyridine wereused.

According to ¹⁹F-NMR analysis of the ether solution, the polymer was acopolymer comprising a fluorine-containing allyl ether having

group and a fluorine-containing allyl ether having OH group in a ratioof 84:16% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 1.

Experimental Examples 14 to 16 Determination of Curing Reactivity by IRAnalysis (1) Preparation of Fluorine-Containing Resin Composition forCoating

Respective coating compositions were prepared using the curablefluorine-containing polymer obtained in Experimental Example 13 by thesame procedures as in Experimental Example 4 so that the concentrationsof the polymer and kinds and amounts of active energy curing initiatorbecame those shown in Table 3.

(2) Production of Film for IR Analysis

The films were produced in the same manner as in Experimental Example 9.

(3) Measurement of Curing Reactivity by IR Analysis

A ratio of curing reaction when light irradiation was carried out in alight irradiation amount of 1,500 mJ/cm² was calculated in the samemanner as in Experimental Example 9. The results are shown in Table 3.

Experimental Example 17

A fluorine-containing resin composition for coating was prepared byadding, as a curing agent,

to the coating composition obtained in Experimental Example 14 so thatthe amount thereof became 20% by weight based on the polymer.

A film for IR analysis was produced using this resin composition in thesame manner as in Experimental Example 14, and a curing reactivity wasdetermined. The results are shown in Table 3.

TABLE 3 Experimental Example 14 15 16 17 Curable fluorine-containingExp. Ex. 13 Exp. Ex. 13 Exp. Ex. 13 Exp. Ex. 13 polymer Content of—O(C═O)CF═CH₂ group 84 84 84 84 (% by mole) Solvent MEK MEK MEK MEKConcentration of polymer 8 8 8 8 (% by weight) Active energy curinginitiator 2-hydroxy-2- 2,2-dimethoxy- Benzophenone 2-hydroxy-2- methyl-2-phenyl- methyl- propiophenone acetophenone propiophenone Proportion topolymer 2.0 2.0 2.0 2.0 (% by weight) Curing agent — — — Polyfunctionalacryl ¹⁾ Proportion to polymer — — — 20 (% by weight) Ratio of curingreaction (%) 73.9 55.0 40.6 84.0 (at 1,500 mJ/cm²) ¹⁾ Polyfunctionalacryl: CH₂═CF(C═O)OCH₂—(CF₂)₆—CH₂O(C═O)CF═CH₂

Preparation Example 2 Synthesis of Homopolymer of Fluorine-ContainingAllyl Ether Having OH Group

Synthesis of a polymer and refining of the obtained polymer were carriedout in the same manner as in Preparation Example 1 except that 20.0 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol)and 10.0 g of a perfluorohexane solution of 8.0% by weight of:

[HCF₂CF₂₃COO₂

were used. Thus 18.2 g of a transparent colorless polymer was obtained.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the obtained polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 30,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was59,000.

Preparation Example 3 Synthesis of Copolymer ComprisingFluorine-Containing Allyl Ether Having OH Group and Vinylidene Fluoride

A 300 ml stainless steel autoclave equipped with a valve, pressure gaugeand thermometer was charged with 34.2 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol),200 g of CH₃CCl₂F (HCFC-141b) and 0.16 g of methanol solution of 50% byweight of dinormalpropyl peroxy carbonate (NPP). While cooling with dryice/methanol solution, the inside of a system was sufficiently replacedwith nitrogen gas. Then 5.8 g of vinylidene fluoride (VdF) wasintroduced through the valve, followed by reaction while shaking at 40°C. With the advance of the reaction, 12 hours after starting of thereaction, a gauge pressure inside the system lowered from 4.4 MPaG (4.5kgf/cm²G) before the reaction to 0.98 MPaG (1.0 kgf/cm²G).

At that time, un-reacted monomer was released and a precipitated solidwas removed and dissolved in acetone, followed by re-precipitation witha solvent mixture of hexane and toluene (50/50) to separate a copolymer.The copolymer was vacuum-dried until a constant weight was reached.Thereby 31.2 g of a copolymer was obtained.

The components of the copolymer were VdF and the fluorine-containingallyl ether having OH group in a ratio of 38:62% by mole according to¹H-NMR and ¹⁹F-NMR analyses. The number average molecular weight of thecopolymer was 12,000 according to the GPC analysis using THF as asolvent and the weight average molecular weight thereof was 18,000.

Experimental Example 18 Synthesis of Fluorine-Containing Active EnergyCuring Initiator

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 2.0 g of2-hydroxy-2-methyl propiophenone, 1.0 g of pyridine and 20 g of amixture (HCFC-225) of CF₃CF₂CHCl/CClF₂CF₂CHClF and was cooled to 5° C.or lower with ice.

Thereto was added dropwise 2.5 g of:

over one hour with stirring in nitrogen gas stream. After completion ofthe addition, the stirring was further continued for 4.0 hours.

After the reaction, the ether solution was put in the dropping funneland washed with 2% hydrochloric acid solution and 5% NaCl solution,followed by separation of an organic layer, drying with anhydrousmagnesium sulfate and distillation to isolate 2.6 g of a product (yield:62%).

According to ¹H-NMR, ¹⁹F-NMR and IR analyses, the product was:

Experimental Example 19 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 40 ml ofmethyl ethyl ketone (MEK), 5.0 g of the fluorine-containing allyl etherhomopolymer having hydroxyl which was obtained in Preparation Example 2and 2.0 g of pyridine, and was cooled to 5° C. or lower with ice.

Thereto was added dropwise 1.2 g of α-fluoroacrylic acid fluoride overabout 30 minutes with stirring in nitrogen gas stream. After completionof the addition, the flask temperature was raised to room temperatureand the stirring was further continued for 4.0 hours.

After the reaction, the MEK solution was put in the dropping funnel andwashed with water, 2% hydrochloric acid solution, 5% NaCl solution andwater, followed by separation of an organic layer and drying withanhydrous magnesium sulfate. A concentration of the polymer afterfiltrating was 10.7% by weight.

According to ¹⁹F-NMR analysis of the MEK solution, the obtained polymerwas a copolymer comprising a fluorine-containing allyl ether having

group and a fluorine-containing allyl ether having OH group in a ratioof 89:11% by mole.

According to IR analysis which was carried out in the same manner as inExperimental Example 1, an absorption of a carbon-carbon double bond andan absorption of C═O group were observed at 1,660 cm⁻¹ and 1,770 cm⁻¹,respectively.

Experimental Example 20 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A curable fluorine-containing polymer (MEK solution) was synthesized inthe same manner as in Experimental Example 19 except that 5.0 g of thecopolymer of the fluorine-containing allyl ether having OH group and VdFwhich was obtained in Preparation Example 3, 1.1 g of pyridine and 1.0 gof α-fluoroacrylic acid fluoride were used. A concentration of thepolymer was 9.9% by weight.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having

group, a fluorine-containing allyl ether having OH group and VdF in aratio of 48:14:38% by mole.

Experimental Example 21 (1) Preparation of Fluorine-Containing ResinComposition for Coating

MEK was added to the curable fluorine-containing polymer (MEK solution)obtained in Experimental Example 19 to adjust the concentration of thepolymer to 8% by weight.

To the MEK solution of the curable fluorine-containing polymer was added2-hydroxy-2-methyl propiophenone as the active energy curing initiatorso that its amount became 2.0% by weight based on the polymer. Howeverthe solution became turbid in white and the both could not be compatiblewith each other.

Therefore the fluorine-containing active energy curing initiatorobtained in Experimental Example 18 was added instead of2-hydroxy-2-methyl propiophenone so that its amount became 3.6% byweight based on the polymer. As a result, a transparent colorlesssolution was obtained and the both were compatible with each other.

(2) Evaluation of Coating Composition

The coating composition containing the fluorine-containing active energycuring initiator was evaluated in the same manner as in (2) to (6) ofExperimental Example 4 (in (2), irradiation of light was carried out at1,500 mJ/cm²), and a ratio of curing reaction when irradiated with lightof 1,500 mJ/cm² was measured in the same manner as in ExperimentalExample 10. The results are shown in Table 4.

Experimental Example 22 (1) Preparation of Fluorine-Containing ResinComposition for Coating

MEK was added to the curable fluorine-containing polymer (MEK solution)obtained in Experimental Example 20 to adjust the concentration of thepolymer to 8% by weight.

To the MEK solution of the curable fluorine-containing polymer was added2-hydroxy-2-methyl propiophenone as the active energy curing initiatorso that its amount became 6.7% by weight based on the polymer. As aresult, a transparent colorless solution was obtained and the both werecompatible with each other.

(2) Evaluation of Coating Composition

The obtained coating composition was evaluated in the same manner as inExperimental Example 21. The results are shown in Table 4.

TABLE 4 Experimental Example 21 22 Substrate film Acryl Acryl Curablefluorine-containing polymer Exp. Ex. 19 Exp. Ex. 20 Content of—O(C═O)CF═CH₂ group 89 48 (% by mole) Solvent MEK MEK Concentration ofpolymer 8 8 (% by weight) Active energy curing agent Fluorine-containing2-hydroxy-2-methyl- initiator of propiophenone Exp. Ex. 18 ²⁾ Proportionto polymer 3.6 6.7 (% by weight) Amount of ultraviolet irradiation 1,5001,500 (mJ/cm²) Ratio of curing reaction (%) 88.7 75.7 (at 1,500 mJ/cm²)Refractive index Before curing 1.368 1.369 After curing 1.375 1.377Reflectance of one side of film (%) 1.40 1.42 Set to touch ◯ ◯ Pencilhardness 2H 2H Solvent resistance ◯ ◯ Abrasion resistance ◯ ◯ 2)

Preparation Example 4 Synthesis of Homopolymer of Fluorine-ContainingAllyl Ether Having OH Group

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 20.8 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol)and 2.2 g of a perfluorohexane solution of 8.0% by weight of:

[HCF₂CF₂₃COO₂

and after the inside of the flask was sufficiently replaced withnitrogen gas, stirring was carried out at 20° C. for 24 hours innitrogen gas stream and a solid having a high viscosity was produced.

The obtained solid was dissolved in diethyl ether and poured intoperfluorohexane, followed by separating and vacuum drying to obtain 19.2g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 72,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was118,000.

Experimental Example 23 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 50 ml ofmethyl ethyl ketone (MEK), 5.0 g of the fluorine-containing allyl etherhomopolymer having hydroxyl which was obtained in Preparation Example 4and 2.5 g of pyridine, and was cooled to 5° C. or lower with ice.

Then a solution obtained by dissolving 2.5 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 10 ml of MEK was added thereto dropwise over aboutten minutes with stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 2.0 hours.

After the reaction, the MEK solution was put in the dropping funnel andwashed with water, 2% hydrochloric acid solution, 5% NaCl solution andwater, followed by drying with anhydrous magnesium sulfate andseparating the solution by filtrating to obtain the MEK solution. Aconcentration of the polymer was 13% by weight.

According to ¹⁹F-NMR analysis of the MEK solution, the polymer was acopolymer comprising a fluorine-containing allyl ether having —OCOCF═CH₂group and a fluorine-containing allyl ether having OH group in a ratioof 70:30% by mole.

The solution was coated on a NaCl plate and formed into a cast film atroom temperature. According to IR analysis of the cast film, anabsorption of a carbon-carbon double bond and an absorption of C═O groupwere observed at 1,661 cm⁻¹ and 1,770 cm⁻¹, respectively.

Experimental Example 24 (1) Preparation of Fluorine-Containing ResinComposition for Coating

MEK was added to the solution of fluorine-containing polymer havingα-fluoroacryloyl group which was obtained in Experimental Example 23 todilute the solution and adjust a concentration of the polymer to 5.0% byweight.

To 10 g of the obtained polymer solution was added, as an active energycuring initiator, 1.2 g of a solution obtained by dissolving2-hydroxy-2-methyl propiophenone in MEK in a concentration of 1% byweight. Thus a uniform solution was obtained.

(2) Production of Antireflection Film

The above-mentioned coating composition was coated on a non-treatedacryl plate at room temperature at 1,000 to 2,000 rpm with a spincoater, followed by drying at 50° C. for five minutes. The number ofrevolutions of the spin coater was adjusted so that a coating thicknessafter the drying became from 90 to 110 nm.

(Light Irradiation)

The coating film after the drying was irradiated with ultraviolet lightat room temperature at an intensity of 1,500 mJ/cm²U using a highpressure mercury lamp.

(3) Measurement of Refractive Index of Curable Fluorine-ContainingPolymer

The solution of fluorine-containing polymer having α-fluoroacryloylgroup which was obtained in Experimental Example 23 was concentrated to50% and coated on a PET film with an applicator so that a coatingthickness after the drying became about 100 μm. After drying at 50° C.for ten minutes, the obtained cast film was peeled from the PET film anda refractive index thereof was measured using an Abbe's refractometer at25° C. with light having a wavelength of 550 nm. The results are shownin Table 5.

(4) Measurement of Refractive Index of Cured Film

The solution of fluorine-containing polymer having α-fluoroacryloylgroup which was obtained in Experimental Example 23 was concentrated to50%, and to 2 g of the solution was added 0.01 g of 2-hydroxy-2-methylpropiophenone as the active energy curing initiator. The obtainedsolution was coated on an aluminum foil with an applicator so that acoating thickness after drying became about 100 μm, followed by dryingat 50° C. for ten minutes. After carrying out the light irradiation inthe same manner as in (2) above, the aluminum foil was melted withdiluted hydrochloric acid to obtain a sample film. A refractive index ofthe obtained cured film was measured in the same manner as in (3) above.The results are shown in Table 5.

(5) Measurement of Reflectance of One Side of Film

The acryl plate having the antireflection film which was obtained in (2)above was set on a visible ultraviolet spectroscope equipped with a 5°regular reflection unit, and a reflectance was measured with lighthaving a wavelength of 550 nm. The results are shown in Table 5.

(6) Evaluation of Physical Properties of Antireflection Film

The following physical properties of the surface of the antireflectionfilm obtained in (2) above were evaluated. The results are shown inTable 5.

{circle around (1)} Pencil Hardness

Measured according to JIS K5400.

{circle around (2)} Solvent Resistance

After the surface of the coating film is rubbed with a cotton clothimpregnated with ethyl acetate, condition (dissolved or peeled) of thefilm surface is evaluated.

When there is no change, it is evaluated as ◯, and when there isdissolution or peeling, it is evaluated as x.

The evaluation is also carried out in the same manner as above withrespect to the case using acetone as a solvent.

{circle around (3)} Abrasion Resistance

A cotton cloth (BEMCOT (Registered trademark) M-3 available from AsahiChemical Co., Ltd.) is fitted to a rubbing tester, and theantireflection film is rubbed by 100 rubbing cycles at a load of 100gf/cm² to observe conditions of the film.

The evaluation is made as follows.

◯: There is no change.Δ: A flaw is found partly.x: There is a portion where a film is peeled and a substrate is seen.{circle around (4)} Scratch Resistance

After the surface of the coating film is rubbed with steel wool #0000,condition of the surface is evaluated.

The evaluation is made as follows.

-   ◯: There is no change.-   Δ: A flaw is found at several parts.-   x: There are many large flaws or the film is peeled and a substrate    is seen.

Experimental Examples 25 to 27

To the coating composition obtained in (1) of Experimental Example 24was added, as a curing agent,

so that its amount became 10% by weight (Experimental Example 25), 30%by weight (Experimental Example 26) and 50% by weight (ExperimentalExample 27) based on the polymer. Antireflection films were produced inthe same manner as in (2) of Experimental Example 24 using therespective coating compositions, and physical properties of theantireflection films were evaluated in the same manner as in (4)Measurement of refractive index of cured film, (5) Measurement ofreflectance of one side of film and (6) Evaluation of physicalproperties of antireflection film. The results are shown in Table 5.

Experimental Example 28 (1) Preparation of Fluorine-Containing ResinComposition for Coating

To 0.5 g of the curing agent:

used in Experimental Example 25 was added 10 g of MEK to dissolve thecuring agent, and thereto was added 1.2 g of a solution obtained bydissolving 2-hydroxy-2-methyl propiophenone as the active energy curinginitiator in a concentration of 1% by weight in MEK to obtain a uniformsolution. An antireflection film was produced in the same manner as in(2) of Experimental Example 24 using the obtained coating composition,and physical properties of the antireflection film were evaluated in thesame manner as in (4) Measurement of refractive index of cured film, (5)Measurement of reflectance of one side of film and (6) Evaluation ofphysical properties of antireflection film. The results are shown inTable 5.

Experimental Example 29

A fluorine-containing resin composition for coating was prepared in thesame manner as in Experimental Example 17 except that

was added as a curing agent in an amount of 30% by weight based on thepolymer. Thereto was added MEK to obtain 5% by weight solution in MEK.An antireflection film was produced in the same manner as in (2) ofExperimental Example 24 using the obtained coating composition, andphysical properties of the antireflection film were evaluated in thesame manner as in (4) Measurement of refractive index of cured film, (5)Measurement of reflectance of one side of film and (6) Evaluation ofphysical properties of antireflection film. The results are shown inTable 5.

Experimental Example 30 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 50 ml of MEK,5.0 g of the copolymer comprising a fluorine-containing allyl etherhaving OH group and VdF and obtained in Preparation Example 3 and 2.2 gof pyridine, and was cooled to 5° C. or lower with ice.

Then a solution obtained by dissolving 2.0 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 10 ml of MEK was added thereto dropwise over aboutten minutes with stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 3.0 hours.

After the reaction, the MEK solution was put in the dropping funnel andwashed with water, 2% hydrochloric acid solution, 5% NaCl solution andwater, followed by drying with anhydrous magnesium sulfate andseparating the MEK solution by filtrating. A concentration of thepolymer was 13.0% by weight.

According to ¹⁹F-NMR analysis of the MEK solution, the polymer was acopolymer comprising a fluorine-containing allyl ether having —OCOCF═CH₂group and VdF in a ratio of 62:38% by mole.

The solution was coated on a NaCl plate and formed into a cast film atroom temperature. According to IR analysis of the cast film, anabsorption of a carbon-carbon double bond and an absorption of C═O groupwere observed at 1,661 cm⁻¹ and 1,770 cm⁻¹, respectively.

Experimental Example 31

(1) Preparation of coating composition, (2) Production of antireflectionfilm and evaluation of coating film were carried out in the same manneras in Experimental Example 24 except that the fluorine-containingpolymer obtained in Experimental Example 30 was used instead of thefluorine-containing polymer having α-fluoroacryloyl group and obtainedin Experimental Example 23 and the fluorine-containing energy curinginitiator obtained in Experimental Example 18 was used as the activeenergy curing initiator instead of 2-hydroxy-2-methyl propiophenone. Theresults are shown in Table 5.

Experimental Example 32

To the coating composition obtained in (1) of Experimental Example 31was added, as a curing agent,

so that its amount became 10% by weight based on the polymer to obtain acomposition for coating. An antireflection film was produced in the samemanner as in (2) of Experimental Example 24 using the obtained coatingcomposition, and (4) Measurement of refractive index of cured film, (5)Measurement of reflectance of one side of film and (6) Evaluation ofphysical properties of antireflection film were carried out in the samemanner. The results are shown in Table 5.

TABLE 5 Experimental Example 24 25 26 27 Substrate film Acryl AcrylAcryl Acryl Curable fluorine-containing Exp. Ex. 23 Exp. Ex. 23 Exp. Ex.23 Exp. Ex. 23 polymer Content of —O(C═O)CF═CH₂ 70 70 70 70 group (% bymole) Crosslinking agent Tetrafunctional Tetrafunctional TetrafunctionalTetrafunctional acryl ¹⁾ acryl ¹⁾ acryl ¹⁾ acryl ¹⁾ Adding amount 0 1030 50 (proportion to polymer (% by weight)) Active energy curing agent2-hydroxy-2- 2-hydroxy-2- 2-hydroxy-2- 2-hydroxy-2- methyl- methyl-methyl- methyl propiophenone propiophenone propiophenone propiophenoneProportion to polymer 2 2 2 2 (% by weight) Amount of ultraviolet 1,5001,500 1,500 1,500 irradiation (mJ/cm²) Refractive index Before curing1.366 — — — After curing 1.374 1.381 1.395 1.432 Reflectance of one sideof 1.4 1.5 1.7 2 % film (%) Pencil hardness 2H 3H 4H 4H Solventresistance ◯ ◯ ◯ ◯ Abrasion resistance ◯ ◯ ◯ ◯ Scratch resistance × Δ ◯◯ Experimental Example 28 29 31 32 Substrate film Acryl Acryl AcrylAcryl Curable fluorine-containing Exp. Ex. 17 Exp. Ex. 30 Exp. Ex. 30polymer Content of —O(C═O)CF═CH₂ Only 84 62 62 group (% by mole)tetrafunctional Crosslinking agent acryl ¹⁾ Bifunctional TetrafunctionalTetrafunctional acryl ³⁾ acryl ¹⁾ acryl ¹⁾ Adding amount 30 0 10(proportion to polymer (% by weight)) Active energy curing agent2-hydroxy-2- 2-hydroxy-2- Fluorine- Fluorine- methyl- methyl- containingcontaining propiophenone propiophenone initiator ²⁾ initiator ²⁾Proportion to polymer 2 2 5 5 (% by weight) Amount of ultraviolet 1,5001,500 1,500 1,500 irradiation (mJ/cm²) Refractive index Before curing —— 1.370 — After curing 1.465 1.390 1.381 1.384 Reflectance of one sideof 3.0 1.6 1.5 1.5 film (%) Pencil hardness 5H 3H 3H 4H Solventresistance ◯ ◯ ◯ ◯ Abrasion resistance ◯ ◯ ◯ ◯ Scratch resistance ◯ Δ Δ◯ ¹⁾ Crosslinking agent (tetrafunctional)

²⁾ Fluorine-containing energy curing initiator

³⁾ Crosslinking agent (bifunctional)

Experimental Example 33 Synthesis of Perfluoropolyether α-Fluoroacrylate

A 500 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 18 g of aperfluoropolyether alcohol:

CF₃CF₂CF₂O(CF₂CF₂CF₂O)_(n)CF₂CF₂CH₂OH (n≈20)

having a linear chain and an average molecular weight of 3,800, 1.0 g ofpyridine and 125 g of 1,1,1,3,3,3-hexafluoromethaxylene, and was cooledto 5° C. or lower with ice.

Thereto was added dropwise a solution obtained by dissolving 0.84 g ofα-fluoroacrylic acid fluoride CH₂═CFCOF in 5 ml of1,1,1,3,3,3-hexafluoromethaxylene over about ten minutes with stirringin nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for four hours.

After the reaction, the ether solution was put in the dropping funneland washed with water, 2% hydrochloric acid solution, 5% NaCl solutionand water, followed by drying with anhydrous magnesium sulfate andseparating the solution by filtrating. After distilling off the solventfrom the filtrate with an evaporator, the solution was dried for sixhours in an evacuated state while heating to 70° C. and thus atransparent colorless liquid having a high viscosity was obtained.

According to ¹H-NMR, ¹⁹F-NMR and IR analyses, the obtained product was

Experimental Examples 34 and 35 Improvement of Surface PhysicalProperties with Compound Having Perfluoropolyether Group (PFPE) (1)Preparation of Fluorine-Containing Resin Composition for Coating

The MEK solutions of fluorine-containing polymer having α-fluoroacryloylgroup which were obtained in Experimental Example 23 (ExperimentalExample 34) and Experimental Example 30 (Experimental Example 35) wereconcentrated to adjust a concentration thereof to 50% by weight,respectively. Then to 2 g of the concentrated MEK solution were added 3g of a CF₃CF₂CHCl/CClF₂CF₂CHClF mixture (HCFC-225), 4 g of MIBK and 6 gof ClCF₂CClFCF₂CCl₂F (CFC-316). Further thereto was added 1.0 g of asolution obtained by dissolving the perfluoropolyether α-fluoroacrylateobtained in Experimental Example 33 in HCFC-225 in a concentration of1.0% by weight.

To the obtained polymer solution was added, as an active energy curinginitiator, 1 g of a solution obtained by dissolving afluorine-containing energy curing initiator in HCFC-225 in aconcentration of 10% by weight, and thus uniform solutions wereobtained.

(2) Production of Antireflection Film

The coating composition obtained above was coated on a non-treated acrylplate at room temperature at 2,000 to 5,000 rpm with a spin coater,followed by drying at 50° C. for five minutes. In that case, the numberof revolutions of the spin coater was adjusted so that a coatingthickness after the drying became from 90 to 110 nm.

(Light Irradiation)

The coating film after the drying was irradiated with ultraviolet lightat room temperature at an intensity of irradiation of 1,500 mJ/cm²Uusing a high pressure mercury lamp.

(3) Measurement of Reflectance of One Side of Film

The acryl plate having the antireflection film which was obtained in (2)above was set on a visible ultraviolet spectroscope equipped with a 5°regular reflection unit, and a reflectance was measured with lighthaving a wavelength of 550 nm. The results are shown in Table 6.

(4) Evaluation of Physical Properties of Antireflection Film

The following physical properties of the surface of the antireflectionfilm obtained in (2) above were evaluated. The results are shown inTable 6.

{circle around (1)} Pencil Hardness

Measured according to JIS K5400.

{circle around (2)} Contact Angle

Contact angles of pure water and n-hexadecane are measured with acontact angle meter.

Experimental Examples 36 and 37

With respect to the antireflection films after the light irradiationwhich were obtained in (2) of Experimental Example 24 (ExperimentalExample 36) and (2) of Experimental Example 31 (Experimental Example37), a contact angle was measured in the same manner as in (4) ofExperimental Example 34. The results are shown in Table 6.

Preparation Example 5 Synthesis of Fluorine-Containing Allyl EtherHomopolymer Having OH Group (and Having Long Side Chain)

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 10.0 g of CH₂═CFCF₂(OCF(CF₃)CF₂)₃OCF(CF₃)CH₂OH and 6.2g of a perfluorohexane solution of 8.0% by weight of:

[HCF₂CF₂₃COO₂

and after the inside of the flask was sufficiently replaced withnitrogen gas, stirring was carried out at 20° C. for 15 hours innitrogen gas stream and a solid having a high viscosity was produced.

The obtained solid was dissolved in diethyl ether and poured intoperfluorohexane, followed by separating and vacuum drying to obtain 7.3g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having hydroxyl atan end of its side chain. The number average molecular weight of thepolymer was 24,000 according to the GPC analysis using tetrahydrofuran(THF) as a solvent and the weight average molecular weight thereof was79,000.

Experimental Example 38 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group (and Having Long Side Chain)

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 50 ml ofmethyl ethyl ketone, 3.0 g of the fluorine-containing allyl etherhomopolymer having hydroxyl which was obtained in Preparation Example 5and 0.4 g of pyridine, followed by cooling to 5° C. or lower with ice.

Then a solution obtained by dissolving 0.55 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 10 ml of methyl ethyl ketone was added theretodropwise over about 10 minutes while stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 2.0 hours.

The ether solution after the reaction was put in the dropping funnel,followed by washing with water, 2% hydrochloric acid solution, 5% NaClsolution and water and then drying with anhydrous magnesium sulfate.Then the methyl ethyl ketone solution was separated by filtration.

According to ¹⁹F-NMR analysis of the methyl ethyl ketone solution, thepolymer was a copolymer comprising a fluorine-containing allyl etherhaving —OCOCF═CH₂ group and a fluorine-containing allyl ether having OHgroup in a ratio of 54:46% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 23.

Experimental Example 39

An antireflection film was produced in the same manner as in (1) and (2)of Experimental Example 24 except that the fluorine-containing polymerof Experimental Example 38 was used instead of the fluorine-containingpolymer having α-fluoroacryloyl group and obtained in ExperimentalExample 23. Physical properties of the antireflection film wereevaluated in the same manner as in (3) and (4) of Experimental Example34. The results are shown in Table 6.

Preparation Example 6 Synthesis of Copolymer ComprisingFluorine-Containing Allyl Ether Having OH Group and Fluorine-ContainingAllyl Ether Having Methyl Ester Structure at an End Thereof

A 100 ml four-necked glass flask equipped with a stirrer and thermometerwas charged with 9.6 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol)and 9.6 g of CH₂═CFCF₂OCF(CF₃) CF₂OCF(CF₃)COOCH₃, followed by stirringsufficiently. Then thereto was added 2.0 g of a perfluorohexane solutionof 8.0% by weight of:

[HCF₂CF₂₃COO₂

and after the inside of the flask was sufficiently replaced withnitrogen gas, stirring was carried out at 20° C. for 20 hours innitrogen gas stream and a solid having a high viscosity was produced.

The obtained solid was dissolved in acetone and poured into aHCFC-225/n-hexane=1/1 solution, followed by separating and vacuum dryingto obtain 15.5 g of a transparent colorless polymer.

According to ¹⁹F-NMR, ¹H-NMR and IR analyses, the product was acopolymer comprising the above-mentioned fluorine-containing allyl etherhaving hydroxyl and fluorine-containing allyl ether having a methylester structure at an end thereof in a ratio of 42:58% by mole. Thenumber average molecular weight of the polymer was 72,000 according tothe GPC analysis using tetrahydrofuran (THF) as a solvent and the weightaverage molecular weight thereof was 117,000.

Experimental Example 40 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 50 ml ofmethyl ethyl ketone, 3.0 g of the fluorine-containing allyl ethercopolymer having hydroxyl which was obtained in Preparation Example 6and 0.6 g of pyridine. Thereto was added dropwise a solution obtained bydissolving 1.0 g of α-fluoroacrylic acid fluoride CH₂═CFCOF in 10 ml ofMEK in the same manner as in Experimental Example 23. Thus a curablefluorine-containing polymer (MEK solution) was synthesized.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having —OCOCF═CH₂ group, afluorine-containing allyl ether having OH group and afluorine-containing allyl ether having a methyl ester structure at anend thereof in a ratio of 38:4:58% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 23.

Experimental Example 41

An antireflection film was produced in the same manner as in (1) and (2)of Experimental Example 31 except that the fluorine-containing polymerof Experimental Example 40 was used instead of the fluorine-containingpolymer having α-fluoroacryloyl group and obtained in ExperimentalExample 30. Then physical properties of the antireflection film wereevaluated in the same manner as in (3) and (4) of Experimental Example34. The results are shown in Table 6.

TABLE 6 Experimental Example 34 35 36 37 39 41 Substrate film AcrylAcryl Acryl Acryl Acryl Acryl Content of end OH group 30 0 30 0 46 4 (%by mole) Adding amount of PFPE 1.0 1.0 None None None None compound ¹⁾(% by weight) Curable fluorine-containing Exp. Ex. 23 Exp. Ex. 30 Exp.Ex. 23 Exp. Ex. 30 Exp. Ex. 38 Exp. Ex. 40 polymer Content of—O(C═O)CF═CH₂ 70 62 — — 54 38 group (% by mole) Active energy curinginitiator Fluorine-containing Fluorine-containing — —Fluorine-containing Fluorine-containing initiator ²⁾ initiator ²⁾initiator 2) initiator 2) Proportion to polymer 10 10 — — 10 10 (% byweight) Amount of ultraviolet irradiation 1,500 mJ 1,500 mJ — — 1,500 mJ1,500 mJ (mJ/cm²) Reflectance of one side of film (%) 1.4 1.5 — — 1.11.4 Pencil hardness 2H 3H — — H 2H Contact angle Water 105.5  98.3 89.595.5 105   93   n-HD 62.8 59.6 50.5 51.7 61.5 54.7 γs 16.1 18.7 23.821.3 16.5 21.6 ¹⁾ PFPE compound

²⁾ Fluorine-containing energy curing initiator

Experimental Examples 42 and 43 Preparation of Fluorine-Containing ResinComposition Possessing Improved Coatability to Pet Film

The MEK solutions of fluorine-containing polymer having α-fluoroacryloylgroup which were obtained in Experimental Example 23 (ExperimentalExample 42) and Experimental Example 30 (Experimental Example 43) wereconcentrated to adjust a concentration thereof to 50% by weight,respectively. Then to 2 g of the concentrated MEK solution were added 14g of MIBK and 4 g of 2,2,3,3-tetrafluoropropanol (HCF₂CF₂CH₂OH). Furtherthereto was added, as an active energy curing initiator, 1.0 g of asolution obtained by dissolving a fluorine-containing energy curinginitiator in HCFC-225 in a concentration of 10% by weight, and thusuniform solutions were obtained.

Experimental Examples 44 and 45 Evaluation of Coatability to PET Film

The coating compositions obtained in Experimental Example 42(Experimental Example 44) and Experimental Example 43 (ExperimentalExample 45) were coated on non-treated PET films, respectively with adoctor blade so that a coating thickness became 2 μM. The coating filmswere observed while air-drying at room temperature. The evaluation wascarried out under the following criteria:

◯: Coating film is dried in a state of uniform coating thickness andthere is no interference pattern after the drying.Δ: Coating film is dried in a state of uniform coating thickness butthere is a small interference pattern after the drying.x: After the coating, repelling of the solution occurs on the PET filmand there are many interference patterns in a concentric form after thedrying. The results are shown in Table 7.

Experimental Examples 46 and 47

MEK was added to the solutions of fluorine-containing polymer havingα-fluoroacryloyl group which were obtained in Experimental Example 23(Experimental Example 46) and Experimental Example 30 (ExperimentalExample 47) to dilute the solutions and adjust the polymer concentrationto 5.0% by weight.

To 20 g of the obtained polymer solution was added, as an active energycuring initiator, 1.0 g of a solution obtained by dissolving thefluorine-containing energy curing initiator obtained in ExperimentalExample 18 in MEK in a concentration of 10% by weight to obtain uniformsolutions. The same evaluation as in Experimental Example 44 was carriedout using the obtained solutions. The results are shown in Table 7.

TABLE 7 Experimental Example 44 45 46 47 Substrate film PET PET PET PETCurable fluorine-containing Exp. Ex. 23 Exp. Ex. 30 Exp. Ex. 23 Exp. Ex.30 polymer Content of —O(C═O)CF═CH₂ group 70 62 70 2 (% by mole) Activeenergy curing initiator Fluorine- Fluorine- Fluorine- Fluorine-containing containing containing containing initiator ¹⁾ initiator ¹⁾initiator ¹⁾ initiator ¹⁾ Proportion to polymer 10 10 10 10 (% byweight) Components of solvent MEK (% by weight)  5  5 100 100 MIBK (% byweight) 74 74  0  0 Fluorine-containing alcohol 21 21  0  0 (% byweight) Coatability on PET ◯ ◯ × Δ ¹⁾ Fluorine-containing energy curinginitiator

Preparation Example 7 Synthesis of Copolymer ComprisingFluorine-Containing Allyl Ether Having OH Group and Tetrafluoroethylene

A 100 ml stainless steel autoclave equipped with a valve, pressure gaugeand thermometer was charged with 10.0 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol),50 g of CH₃CCl₂F (HCFC-141b) and 0.1 g of a methanol solution of 50% byweight of dinormalpropyl peroxy carbonate (NPP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling with adry ice/methanol solution. Then 8.0 g of tetrafluoroethylene (TFE) wasintroduced through the valve. After completion of the reaction carriedout for 14 hours while shaking at 40° C., un-reacted monomer wasreleased to terminate the reaction.

A precipitated solid was removed and dissolved in acetone, followed byre-precipitation with a solvent mixture of hexane and HCFC-225 (20/80)to separate a copolymer. The copolymer was vacuum-dried until a constantweight was reached. Thus 9.3 g of the copolymer was obtained.

According to ¹⁹F-NMR and ¹H-NMR analyses, components of the copolymerwere TFE and the fluorine-containing allyl ether having OH group in aratio of 48:52% by mole. The number average molecular weight of thepolymer was 24,000 according to the GPC analysis using THF as a solventand the weight average molecular weight thereof was 36,100.

Preparation Example 8 Synthesis of Copolymer ComprisingFluorine-Containing Allyl Ether Having OH Group andChlorotrifluoroethylene

A 100 ml stainless steel autoclave equipped with a valve, pressure gaugeand thermometer was charged with 10.0 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol),50 g of CH₃CCl₂F (HCFC-141b) and 0.1 g of a methanol solution of 50% byweight of dinormalpropyl peroxy carbonate (NPP), and the inside of asystem was sufficiently replaced with nitrogen gas while cooling with adry ice/methanol solution. Then 5.8 g of chlorotrifluoroethylene (CTFE)was introduced through the valve. After completion of the reactioncarried out for 20 hours while shaking at 40° C., un-reacted monomer wasreleased to terminate the reaction.

A precipitated solid was removed and dissolved in acetone, followed byre-precipitation with a solvent mixture of hexane and HCFC-141b (50/50)to separate a copolymer. The copolymer was vacuum-dried until a constantweight was reached. Thus 5.7 g of the copolymer was obtained.

According to ¹⁹F-NMR and ¹H-NMR analyses, components of the copolymerwere CTFE and the fluorine-containing allyl ether having OH group in aratio of 35:65% by mole. The number average molecular weight of thepolymer was 10,500 according to the GPC analysis using THF as a solventand the weight average molecular weight thereof was 7,200.

Experimental Example 48 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 50 ml ofdiethyl ether, 2.0 g of the fluorine-containing allyl ether copolymerhaving hydroxyl which was obtained in Preparation Example 7 and 0.9 g ofpyridine. Thereto was added dropwise a solution obtained by dissolving0.9 g of α-fluoroacrylic acid fluoride CH₂═CFCOF in 10 ml of diethylether in the same manner as in Experimental Example 23. Thus a curablefluorine-containing polymer (diethyl ether solution) was synthesized.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having —OCOCF═CH₂ group and TFE in aratio of 52:48% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 23.

Experimental Example 49 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 30 ml ofmethyl isobutyl ketone, 3.0 g of the fluorine-containing allyl ethercopolymer having hydroxyl which was obtained in Preparation Example 8and 0.7 g of pyridine. Thereto was added dropwise a solution obtained bydissolving 0.8 g of α-fluoroacrylic acid fluoride CH₂═CFCOF in 10 ml ofmethyl isobutyl ketone in the same manner as in Experimental Example 23.Thus a curable fluorine-containing polymer (methyl isobutyl ketonesolution) was synthesized.

According to ¹⁹F-NMR analysis, the polymer was a copolymer comprising afluorine-containing allyl ether having —OCOCF═CH₂ group, afluorine-containing allyl ether having OH group and CTFE in a ratio of50:15:35% by mole.

According to IR analysis, an absorption of a carbon-carbon double bondand an absorption of C═O group were observed at the same positions,respectively as in Experimental Example 23.

Experimental Examples 50 and 51

Refractive indices of curable fluorine-containing polymers before andafter curing were measured in the same manner as in (3) and (4) ofExperimental Example 24 except that the fluorine-containing polymershaving α-fluoroacryloyl group which were obtained in ExperimentalExample 48 (Experimental Example 50) and Experimental Example 49(Experimental Example 51) were used instead of the curablefluorine-containing polymer obtained in Experimental Example 23. Theresults are shown in Table 8.

TABLE 8 Experimental Example 50 51 Curable fluorine- Exp. Ex. 48 Exp.Ex. 49 containing polymer Content of —O(CO)CF═CH₂ 52 50 group Refractiveindex Before curing 1.363 1.368 After curing 1.374 1.380

Experimental Example 52 Synthesis of Novel Fluorine-ContainingUnsaturated Compound

A 200 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 20.4 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol):

80 ml of diethyl ether and 4.3 g of pyridine, and was cooled to 5° C. orlower with ice.

Then a solution obtained by dissolving 5.1 g of α-fluoroacrylic acidfluoride CH₂═CFCOF in 20 ml of diethyl ether was added thereto dropwiseover about 30 minutes with stirring in nitrogen gas stream.

After completion of the addition, the flask temperature was raised toroom temperature and the stirring was further continued for 4.0 hours.

After the reaction, the ether solution was poured in an excessive amountof water and an organic substance was extracted with ether, followed bywashing of the ether layer with water, 2% hydrochloric acid solution, 5%NaCl solution and then water, drying the ether layer with anhydrousmagnesium sulfate and distilling off the ether to obtain 23 g of anorganic substance.

According to ¹H-NMR, ¹⁹F-NMR and GC-Mass analyses, the obtained productwas recognized to be a novel fluorine-containing unsaturated compoundrepresented by:

According to IR analysis, two absorptions of carbon-carbon double bondwere observed at 1,661 cm⁻¹ and 1,695 cm⁻¹ and an absorption of C═Ogroup was observed at 1,770 cm⁻¹.

Preparation Example 9

A 300 ml four-necked flask equipped with a reflux condenser,thermometer, stirrer and dropping funnel was charged with 46.4 g of2,3,3,5,6,6,8-pentafluoro-4,7,10-trioxa-5,8-bistrifluoromethyl-12,13-epoxytrideca-1-ene:

20 g of acetic acid and 1.0 g of triethylamine, followed by heating at95° to 105° C. for four hours with stirring.

After cooling to room temperature, a solution obtained by mixing 10.0 gof 85% potassium hydroxide and 80 ml of methanol was added dropwise overabout 30 minutes at room temperature through the dropping funnel. Aftercompletion of the addition, stirring was carried out at room temperaturefor five hours.

After completion of the reaction, 44 ml of 17% hydrochloric acidsolution was added and the mixture was poured in a large amount ofwater. Thereafter sodium bicarbonate was added until the aqueous layerbecame neutral.

After neutralizing, washing with 5% NaHCO₃ solution and water wererepeated. After drying of an ether layer with anhydrous magnesiumsulfate, the ether was distilled off to obtain 29 g of an organicsubstance.

According to ¹H-NMR, ¹⁹F-NMR, IR and Mass analyses, the obtained productwas a fluorine-containing allyl ether compound having two hydroxylgroups and represented by the formula:

Experimental Example 53 Synthesis of Novel Fluorine-ContainingUnsaturated Compound

Reaction and isolation were carried out in the same manner as inExperimental Example 52 except that 24.1 g of the fluorine-containingallyl ether compound having two hydroxyl groups which was obtained inPreparation Example 9 and represented by:

was used instead ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol and8.3 g of pyridine and 10.2 g of α-fluoroacrylic acid fluoride CH₂═CFCOFwere used. Thus 19.0 g of an organic substance was obtained.

According to ¹H-NMR, ¹⁹F-NMR and GC-Mass analyses, the obtained productwas a novel fluorine-containing unsaturated compound represented by theformula:

According to IR analysis, two absorptions of carbon-carbon double bondwere observed at 1,661 cm⁻¹ and 1,695 cm⁻¹ and an absorption of C═Ogroup was observed at 1,770 cm⁻¹.

Preparation Example 10 Synthesis of Fluorine-Containing Allyl EtherHomopolymer Having Hydroxyl

Polymerization and refining of a polymer were carried out in the samemanner as in Preparation Example 1 except that 24.1 g of thefluorine-containing allyl ether compound having two hydroxyl groupswhich was obtained in Preparation Example 9 and represented by:

was used instead ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol.Thus 13.5 g of a transparent colorless polymer was obtained.

According to ¹H-NMR, ¹⁹F-NMR and IR analyses, the obtained polymer was afluorine-containing polymer consisting of the structural unit of theabove-mentioned fluorine-containing allyl ether and having two OH groupsat each side chain.

Experimental Example 54 Synthesis of Curable Fluorine-Containing PolymerHaving α-Fluoroacryloyl Group)

Synthesis of a curable fluorine-containing polymer was carried out inthe same manner as in Experimental Example 1 except that 4.8 g of thefluorine-containing allyl ether homopolymer having OH groups at eachside chain and obtained in Preparation Example 10 was used instead ofthe fluorine-containing allyl ether polymer having hydroxyl and obtainedin Preparation Example 1, and 3.1 g of pyridine and 2.0 g ofα-fluoroacrylic acid fluoride were used.

According to ¹⁹F-NMR analysis of the obtained ether solution, thepolymer was a polymer consisting of a structural unit derived from thefluorine-containing allyl ether represented by the formula:

The polymer was coated on a NaCl plate and formed into a cast film atroom temperature. According to IR analysis, an absorption of acarbon-carbon double bond was observed at 1,660 cm⁻¹ and an absorptionof C═O group was observed at 1,770 cm⁻¹. However an absorption of OHgroup could not be observed.

INDUSTRIAL APPLICABILITY

According to the present invention, there can be provided a curablefluorine-containing polymer which can realize a high hardness byphoto-curing while maintaining a low refractive index.

Further there can be provided an antireflection film possessing improvedscratch resistance and abrasion resistance while maintaining areflection reducing effect, and an antireflection-treated articleprovided with such an antireflection film can be provided.

1. A curable fluorine-containing polymer which has a number averagemolecular weight of from 500 to 1,000,000 and is represented by theformula (1):MA  (1) in which the structural unit M is a structural unit derivedfrom fluorine-containing ethylenic monomer and represented by theformula (M):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; b and c are the same or different and each is 0 or 1, the structuralunit A is a structural unit derived from monomer copolymerizable withthe fluorine-containing ethylenic monomer represented by the formula(M), said polymer comprises from 0.1 to 100% by mole of the structuralunit M and from 0 to 99.9% by mole of the structural unit A.
 2. Acurable fluorine-containing polymer which has a number average molecularweight of from 500 to 1,000,000 and is represented by the formula (1-1):MA1A2  (1-1) in which the structural unit M is the same structuralunit as said formula (M), the structural unit A1 is a structural unitrepresented by the formula (A1):

wherein X¹¹, X¹² and X¹³ are the same or different and each is H or F;X¹⁴ is H, F or CF₃; h is 0, 1 or 2; i is 0 or 1; Rf⁴ is afluorine-containing alkylene group having 1 to 40 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andether bond; Z¹ is selected from —OH, —CH₂OH, —COOH, carboxylic acidderivative, —SO₃H, sulfonic acid derivative, epoxy group and cyanogroup, the structural unit A2 is a structural unit represented by theformula (A2):

wherein X¹⁵, X¹⁶ and X¹⁸ are H or F; X¹⁷ is H, F or CF₃; h1, i1 and jare 0 or 1; Z² is H, F or Cl; Rf⁵ is a fluorine-containing alkylenegroup having 1 to 20 carbon atoms or a fluorine-containing alkylenegroup having 2 to 100 carbon atoms and ether bond, said polymercomprises from 0.1 to 90% by mole of the structural unit M, from 0 to99.9% by mole of the structural unit A1 and from 0 to 99.9% by mole ofthe structural unit A2 and contains from 10 to 99.9% by mole of A1+A2.3. The curable fluorine-containing polymer of claim 1, wherein at leastone Y¹ is bonded to an end of Rf.
 4. The curable fluorine-containingpolymer of claim 1, wherein in the formula (1) or (1-1), the structuralunit M is a structural unit M1 derived from fluorine-containingethylenic monomer and represented by the formula (M1):

wherein X¹ and X² are the same or different and each is H or F; X³ is H,F, CH₃ or CF₃; X⁴ and X⁵ are the same or different and each is H, F orCF₃; Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to3; c is 0 or
 1. 5. The curable fluorine-containing polymer of claim 1,wherein in the formula (1) or (1-1), the structural unit M is astructural unit M2 derived from fluorine-containing ethylenic monomerand represented by the formula (M2):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y′ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 6. The curable fluorine-containingpolymer of claim 1, wherein in the formula (1) or (1-1), the structuralunit M is a structural unit M3 derived from fluorine-containingethylenic monomer and represented by the formula (M3):

wherein Rf is an organic group in which 1 to 3 of Y¹ (Y¹ is a monovalentorganic group having 2 to 10 carbon atoms and an ethylenic carbon-carbondouble bond at its end) are bonded to a fluorine-containing alkyl grouphaving 1 to 40 carbon atoms or a fluorine-containing alkyl group having2 to 100 carbon atoms and ether bond.
 7. The curable fluorine-containingpolymer of claim 1, wherein Y¹ is an organic group represented by theformula:O_(d)C═O)_(e)—Y² wherein Y² is an alkenyl group orfluorine-containing alkenyl group having 2 to 5 carbon atoms and anethylenic carbon-carbon double bond at an end thereof; d and e are thesame or different and each is 0 or
 1. 8. The curable fluorine-containingpolymer of claim 1, wherein Y¹ is represented by the formula:—O(C═O)CX⁶═CX⁷X⁸ wherein X⁶ is H, F, CH₃ or CF₃; X⁷ and X⁸ are the sameor different and each is H or F.
 9. The curable fluorine-containingpolymer of claim 2, wherein in the formula (1-1), the structural unit(A1) is represented by the formula (A1-1):

wherein Rf⁴ and Z¹ are as defined in the formula (A1).
 10. The curablefluorine-containing polymer of claim 2, wherein in the formula (1-1),the structural unit (A1) is represented by the formula (A1-2):

wherein Rf⁴ and Z¹ are as defined in the formula (A1).
 11. The curablefluorine-containing polymer of claim 2, wherein in the formula (1-1),the structural unit (A2) is a structural unit derived from at least onemonomer selected from tetrafluoroethylene, vinylidene fluoride,chlorotrifluoroethylene and hexafluoropropylene.
 12. The curablefluorine-containing polymer of claim 2, wherein the polymer of theformula (1-1) comprises from 10 to 80% by mole of the structural unit M,from 1 to 60% by mole of the structural unit A1 and from 20 to 85% bymole of the structural unit A2 and contains from 20 to 90% by mole ofA1+A2.
 13. The curable fluorine-containing polymer of claim 1, which hasa refractive index of not more than 1.40.
 14. The curablefluorine-containing polymer of claim 1, which is soluble in at least onesolvent selected from the group consisting of ketone solvents, aceticacid ester solvents, alcohol solvents and aromatic hydrocarbon solvents.15-49. (canceled)